JP7324584B2 - Method for producing dialkoxymagnesium, method for producing solid catalyst component for olefin polymerization, method for producing catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing dialkoxymagnesium as a carrier raw material for a catalyst component for olefin polymerization. The present invention also relates to a solid catalyst component for olefin polymerization, a solid catalyst for olefin polymerization, and a method for producing an olefin polymer.

Conventionally, as a method for polymerizing olefins, there exists an olefin polymerization catalyst comprising a solid catalyst component obtained by bringing dialkoxymagnesium, a titanium halogen compound and an internal electron donor compound into mutual contact, and an organoaluminum compound. Many methods for polymerizing olefins for polymerizing or copolymerizing olefins have been proposed.

In such a method for polymerizing olefins, the shape of the resulting polyolefin depends on the shape of the solid catalyst component used for polymerization. Therefore, it is important to control the morphology (particle structure) of the solid catalyst component. is done.

Under such circumstances, in the polymerization of olefins, a narrow particle size distribution is required as a requirement for controlling the shape of polyolefin polymer particles. In order to obtain polyolefin with a narrow particle size distribution, a solid catalyst component with a narrow particle size distribution is required.

Here, the particle structure of the solid catalyst component depends on the particle structure of the dialkoxymagnesium serving as the support for the solid catalyst component. In other words, dialkoxymagnesium with a narrow particle size distribution is required in order to obtain a polyolefin with a narrow particle size distribution.

The solid catalyst component for olefin polymerization also affects the BD (Bulk Density) of the resulting olefin polymer. If the BD of the solid catalyst component for the polymerization of olefins is too low, the weight per unit volume will decrease, resulting in a large volume for the reaction and subsequent storage. Since the holding power of the coalescence (rubber component) inside the particles is lowered, the particle surfaces become sticky and the fluidity of the copolymer is lowered. For these reasons, it is also required that the BD (bulk specific gravity) of the solid catalyst component for olefin polymerization is in an appropriate range.

Further, when the solid catalyst component for olefin polymerization is produced, if the raw material, dialkoxymagnesium, is fragile particles, a large amount of fine powder is generated, and this fine powder precipitates during the production of the solid catalyst component. In addition to poor performance and a decrease in the yield of the solid catalyst component obtained, when olefins are polymerized with the solid catalyst component obtained using such a carrier, in the system A polymer with a large amount of fine powder is likely to be generated, which causes adhesion and clogging in the system. Therefore, the dialkoxymagnesium used as a raw material for the solid catalyst component for olefin polymerization is also required to be resistant to breakage.

As a method for producing dialkoxymagnesium, for example, in Patent Document 1, particulate metallic magnesium having an average particle size of 50 μm to 500 μm and 0.25 to 2.5 mol % of an aliphatic branched alcohol having 3 to 4 carbon atoms are used. Direct solid-liquid reaction with mixed alcohol with ethyl alcohol containing, the amount of alkoxide derived from aliphatic branched alcohol having 3 to 4 carbon atoms contains more than a detectable amount, but the content in all alkoxides is less than 2.5 mol%, the remaining alkoxide is ethoxide, the average particle size indicated by D ₅₀ is 10 to 70 μm, the bulk density is 0.25 to 0.50 g / ml, and the particle strength is A process for the synthesis of mixed magnesium dialkoxide granules having a 2.5-6.0 MPa measured by defined method is disclosed.

Further, in Patent Document 2, in a method of synthesizing magnesium alcoholate by directly reacting metallic magnesium and an alcohol represented by the general formula ROH in the absence of a solvent and in the presence of a catalyst, final The addition ratio is metal magnesium/alcohol (weight ratio) = 1/9 to 15, and the final addition ratio of metal magnesium and alcohol is continuously or intermittently added to the reaction system under reflux of the alcohol, and the mixture is 5 to 80. A method for synthesizing spherical magnesium alcoholates with a narrow particle size distribution is disclosed, which is characterized by reacting for 1 minute and then performing an aging reaction under reflux of the alcohol.

Further, Patent Documents 3 and 4 disclose a method of reacting metal magnesium and alcohol in the presence of iodine as a reaction accelerator, in which iodine as a reaction accelerator is added to the reaction system in multiple portions. disclosed.

Japanese Unexamined Patent Application Publication No. 2012-171957 JP-A-3-74341 JP 2013-95890 A WO2013/058193

However, the production methods of Patent Documents 1 to 4 cannot provide dialkoxymagnesium that simultaneously satisfies all of the requirements of narrow particle size distribution, high BD, and resistance to breaking of particles. If the BD is low, the volume of the reaction and subsequent storage becomes large, so the BD is preferably high. However, if the BD is too high, the holding power of the copolymer (rubber component) inside the particles will be low, and the particle surfaces will become sticky. is required.

Accordingly, an object of the present invention is to provide a method for producing dialkoxymagnesium for obtaining dialkoxymagnesium with a narrow particle size distribution, a high BD, and particles that are difficult to break.

In such a situation, the present inventors have made extensive studies, and as a result, when metallic magnesium and alcohol are reacted, halogen is used as a reaction accelerator, and when metallic magnesium is added in portions, it is added to the reaction vessel. By adjusting the ratio of metallic magnesium and alcohol, the inventors have found that dialkoxymagnesium with a narrow particle size distribution, a small BD, and particles that are difficult to break can be obtained, leading to the completion of the present invention.

That is, the present invention (1) is a method for producing dialkoxymagnesium in which dialkoxymagnesium is obtained by reacting metallic magnesium with an alcohol in the presence of a reaction accelerator,
using iodine (I ₂ ) as the reaction accelerator;
that the alcohol is ethanol;
adding the metallic magnesium to the reaction vessel in multiple batches;
The molar ratio (iodine/magnesium metal) of the total amount (mol) of iodine (I ₂ ) added as the reaction accelerator to the total amount (mol) of magnesium metal is 0.001 to 0.008. ,
A value is defined as the amount of metallic magnesium in the reaction vessel at the start of the reaction (kg)/the amount of alcohol in the reaction vessel at the start of the reaction (m ³ ). After the total amount of metallic magnesium added to the container (kg)/the generation rate S (liters/minute) of hydrogen produced by the reaction after the operation of adding metallic magnesium from the beginning to the end increases to its maximum value, 45 of said maximum value %, when the value of the total addition amount (m ³ ) of alcohol added to the reaction vessel is defined as the B value, the A value is 5.0 to 50.0, and the B value is 40.0 to 70.0 and the ratio of the B value to the A value (B value/A value) is 2.10 to 8.50,
To provide a method for producing dialkoxymagnesium characterized by

Further, according to the present invention (2), the method for producing a dialkoxymagnesium of (1) is performed to obtain a dialkoxymagnesium, and then the obtained dialkoxymagnesium (a), a titanium halogen compound (b), and an electron A method for producing a solid catalyst component for polymerization of olefins, characterized by obtaining a solid catalyst component for polymerization of olefins by contacting with a donor compound (c).

In the present invention (3), the method for producing a solid catalyst component for polymerization of olefins of (A)(2) is performed to obtain a solid catalyst component for polymerization of olefins, and then the obtained solid catalyst for polymerization of olefins is obtained. Provided is a process for producing an olefin polymerization catalyst, which comprises bringing components (B) an organoaluminum compound and (C) an external electron-donating compound into contact with each other to obtain an olefin polymerization catalyst. is.

Further, according to the present invention ( 4 ), the (B) organoaluminum compound has the following general formula (2):
R ² _p AlQ _3-p (2)
(In the formula, R ² represents an alkyl group having 1 ^to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0<p≦3. ² may be the same or different, and when there are multiple Qs, each Q may be the same or different.)
The present invention provides a method for producing an olefin polymerization catalyst according to ( 3 ), which is an organoaluminum compound represented by:

Further, according to the present invention ( 5 ), the (C) external electron donating compound has the following general formula (3):
R ³ _q Si(OR ⁴ ) _4-q (3)
(wherein R ³ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, a carbon represents an aromatic hydrocarbon group of 6 to 15 carbon atoms or an aromatic hydrocarbon group of 6 to 15 carbon atoms having a substituent, and when a plurality of R ³ are present, the plurality of R ³ may be the same or different; R ⁴ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent; is an aromatic hydrocarbon group having 7 to 12 carbon atoms, and when a plurality of R ⁴ are present, the plurality of R ⁴ may be the same or different, and q is an integer of 0≦q≦3. )
and an organosilicon compound represented by the general formula (4):
(R ⁵ R ⁶ N) _s SiR ⁷ _4-s (4)
(wherein R ⁵ and R ⁶ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ⁵ and R ⁶ may be the same or different, and may be combined to form a ring, and R ⁵ R ⁶ N group are present, the plurality of R ⁵ R ⁶ N groups may be the same or different, and ^{R 7} is an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, a vinyloxy group, an alkenyloxy group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyloxy group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, represents an aryloxy group having 6 to 20 carbon atoms, and when a plurality of R ⁷ are present, the plurality of R ⁷ may be the same or different, and s is an integer of 1 to 3.)
The present invention provides a method for producing an olefin polymerization catalyst according to ( 3 ) or ( 4 ), characterized in that it is one or more selected from aminosilane compounds represented by the following.

Further, the present invention (6) is a method for producing an olefin polymerization catalyst according to any one of (3) to (5) to obtain an olefin polymerization catalyst, and then the presence of the obtained olefin polymerization catalyst. The present invention provides a method for producing an olefin polymer, characterized in that the olefin is polymerized as follows.

According to the present invention, it is possible to provide a method for producing dialkoxymagnesium for obtaining dialkoxymagnesium having a narrow particle size distribution, a high BD, and particles that are difficult to break.

The method for producing dialkoxymagnesium of the present invention is a method for producing dialkoxymagnesium in which dialkoxymagnesium is obtained by reacting metallic magnesium with alcohol in the presence of a reaction accelerator,
using a halogen as the reaction accelerator;
adding the magnesium metal in multiple portions to the reaction vessel;
A value is defined as the amount of metallic magnesium in the reaction vessel at the start of the reaction (kg)/the amount of alcohol in the reaction vessel at the start of the reaction (m ³ ). After the total amount of metallic magnesium added to the container (kg)/the generation rate S (liters/minute) of hydrogen produced by the reaction after the operation of adding metallic magnesium from the beginning to the end increases to its maximum value, 45 of said maximum value %, the ratio of the B value to the A value (B value/A value) is 2.0%, where B is the total amount of alcohol added to the reaction vessel (m ³ ). 10 to 8.50;
A method for producing dialkoxymagnesium characterized by

The method for producing dialkoxymagnesium of the present invention is a method for producing dialkoxymagnesium in which dialkoxymagnesium is obtained by reacting metallic magnesium with alcohol in the presence of a reaction accelerator.

The shape of metallic magnesium in the method for producing dialkoxymagnesium of the present invention is not particularly limited, and examples thereof include granular, ribbon-like, and powdery shapes. Among these, powdered magnesium is preferable, and the average particle size of the powdered metallic magnesium is preferably 10 to 1000 μm, 20 to 800 μm, and particularly preferably 50 to 500 μm. The surface condition of metallic magnesium is not particularly limited, but it is preferable that a film such as magnesium oxide is not formed on the surface. The content of fine powder components having an average particle size of less than 5 μm in metallic magnesium is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. The content of the coarse powder component is preferably 10% by mass or less, more preferably 5% by mass or less.

The alcohol used in the method for producing dialkoxymagnesium of the present invention is not particularly limited. For example, lower alcohols having 1 to 6 carbon atoms such as methanol, ethanol, propanol, butanol and hexanol are preferred, and ethanol is particularly preferred. The water content of the alcohol is not particularly limited, but the lower the water content, the more preferable, and anhydrous alcohol or dehydrated alcohol having a water content of 200 ppm or less is particularly preferable.

The reaction accelerator used in the method for producing dialkoxymagnesium of the present invention is halogen. Halogen includes I ₂ , I—Cl, I—Br, and the like. Among these, _I2 is preferable as the reaction accelerator. By using a halogen as the reaction accelerator, the particle size distribution index (SPAN) can be narrowed.

In the method for producing dialkoxymagnesium of the present invention, metallic magnesium is added in multiple batches to the reaction vessel. That is, in the method for producing dialkoxymagnesium of the present invention, the total metallic magnesium to be added to the reaction vessel is divided into two or more portions, and the divided metallic magnesium is added to the reaction vessel in multiple portions.

In the method for producing dialkoxymagnesium of the present invention, among multiple divided additions of metallic magnesium, the divided addition up to the start of the reaction is performed at a temperature lower than the reaction temperature, preferably 60° C. or lower, particularly preferably 50° C. or lower. , adding metallic magnesium to the reaction vessel. In addition, the time at which the reaction is initiated refers to the first time at which the reaction temperature of metallic magnesium and alcohol is reached during the entire reaction process. Further, in the method for producing dialkoxymagnesium of the present invention, among the multiple divided additions of metallic magnesium, in the divided addition after the start of the reaction, the temperature range from 10 ° C. higher than the reaction temperature to the reaction temperature Add metallic magnesium to

In the method for producing dialkoxymagnesium of the present invention, the alcohol is added to the reaction vessel in multiple batches. That is, in the method for producing dialkoxymagnesium of the present invention, the total alcohol to be added to the reaction vessel is divided into two or more, and the divided alcohol is added to the reaction vessel in multiple batches.

In the method for producing dialkoxymagnesium of the present invention, the reaction accelerator may be added in its entirety at once, or may be added in multiple batches.

In the method for producing dialkoxymagnesium according to the present invention, the molar ratio (halogen/metal magnesium) of the total amount (mol) of halogen added as a reaction accelerator to the total amount (mol) of metallic magnesium is preferably 0.5. 001 to 0.008, particularly preferably 0.002 to 0.005. When the molar ratio (halogen/metal magnesium) of the total amount (mol) of halogen added as a reaction accelerator to the total amount (mol) of metallic magnesium is within the above range, the shape, bulk specific gravity, and particle size distribution are good. dialkoxymagnesium.

In the method for producing dialkoxymagnesium of the present invention, examples of the operation mode for adding metal magnesium, alcohol and reaction accelerator to the reaction vessel before the start of the reaction include the following operation modes.
(i) An operation of first adding metallic magnesium to an empty reaction vessel, then adding one of the alcohol and the reaction accelerator, and then adding the other of the alcohol and the reaction accelerator. .
(ii) An operation of first adding a reaction accelerator to an empty reaction vessel, then adding one of metallic magnesium and alcohol, and then adding the other of metallic magnesium and alcohol.
(iii) To an empty reaction vessel, first add the alcohol, then add one of the magnesium metal and the accelerator, and then add the other of the magnesium metal and the accelerator. operation.

In the method for producing dialkoxymagnesium of the present invention, after the reaction has started and after the final addition of metallic magnesium, the generation rate S (liters/minute) of hydrogen produced by the reaction has increased to its maximum value. Examples of the mode of addition for adding metal magnesium, alcohol, and reaction accelerator to the reaction vessel until the point of time when the concentration drops to 45% of the maximum value include the following modes of operation.
(i) An operation of adding only metallic magnesium to the reaction vessel.
(ii) An operation of adding only alcohol to the reaction vessel.
(iii) An operation of adding only the reaction accelerator to the reaction vessel.
(iv) An operation of adding a mixture of metallic magnesium and alcohol to the reaction vessel.
(v) An operation of adding a mixture of metallic magnesium and a reaction accelerator to the reaction vessel.
(vi) An operation of adding a mixture of alcohol and a reaction accelerator to the reaction vessel.
(vii) An operation of adding a mixture of metallic magnesium, alcohol and a reaction accelerator to the reaction vessel.

Then, in the method for producing dialkoxymagnesium of the present invention, metal magnesium and alcohol are stirred and in the presence of a reaction accelerator, in a suspension state in which metal magnesium is dispersed in alcohol, these reactions are carried out. conduct.

In the method for producing dialkoxymagnesium of the present invention, the value of "the amount of metallic magnesium in the reaction vessel at the start of the reaction (kg)/the amount of alcohol in the reaction vessel at the start of the reaction (m ³ )" is defined as the A value, and " Total amount (kg) of metallic magnesium added to the reaction vessel from the "first" to the "final metallic magnesium addition operation" / generation rate S of hydrogen generated by the reaction after the "initial" to "final metallic magnesium addition operation" liters/min) increases to its maximum value and then decreases to 45% of said maximum value, the total amount of alcohol added to the reaction vessel (m ³ )” is defined as the value of B. Furthermore, the ratio of the B value to the A value (B value/A value) is 2.10 to 8.50.

The A value is a value calculated from "the amount of metallic magnesium in the reaction vessel at the start of the reaction (kg)/the amount of alcohol in the reaction vessel at the start of the reaction (m ³ )". In other words, the A value is calculated by "addition amount (kg) of metallic magnesium added to the reaction vessel before starting the reaction/addition amount (m ³ ) of alcohol added to the reaction vessel before starting the reaction". is the value to be Further, the B value is defined as "the total amount of metallic magnesium added to the reaction vessel from the beginning to the final metallic magnesium addition operation (kg) / the generation rate S of hydrogen generated by the reaction after the initial to the final metallic magnesium addition operation ( liters/min) increases to its maximum value and then decreases to 45% of its maximum value, the value is calculated by the total addition of alcohol (m ³ ) added to the reaction vessel. In other words, the B value is "the total amount (kg) of metallic magnesium added to the reaction vessel from the initial to the final metallic magnesium addition operation/the initial addition to the metallic magnesium addition operation to the reaction vessel. The total amount of alcohol (m ³ )” is a value calculated by

In addition, in the method for producing dialkoxymagnesium of the present invention, after the final operation of adding metallic magnesium and after the final operation of adding metallic magnesium, the generation rate S (liters/minute) of hydrogen generated by the reaction increases to its maximum value. After that, alcohol alone may be added to the reaction vessel until the point at which it drops to 45% of the maximum value. In this case, in the calculation of the B value, "the generation rate S (liters/minute) of hydrogen produced by the reaction after the initial to final metallic magnesium addition operation increases to its maximum value, and then reaches 45% of the maximum value. "Total amount of alcohol to be added to the reaction vessel" until the point of decrease, after the final metallic magnesium addition operation and after the final metallic magnesium addition operation, the hydrogen generation rate S (liter / minute) generated by the reaction Include the amount of alcohol added in the operation in which only alcohol was added to the reaction vessel after the step increased to its maximum value until it dropped to 45% of its maximum value.

On the other hand, in the method for producing dialkoxymagnesium of the present invention, the generation rate S (liters/minute) of hydrogen generated by the reaction after the final metallic magnesium addition operation and after the final metallic magnesium addition operation increases to its maximum value. After that, the alcohol alone may be added to the reaction vessel after the time when it drops to 45% of the maximum value, but in this case, in the calculation of the B value, "from the beginning to the end of the metallic magnesium addition operation, the reaction After the rate S (liters/minute) of hydrogen produced by increasing to its maximum value, by the time point when it decreases to 45% of said maximum value, the total amount of alcohol added to the reaction vessel (m ³ ) 45% of the maximum value after the final metallic magnesium addition operation and after the generation rate S (liters/minute) of hydrogen generated by the reaction after the final metallic magnesium addition operation increases to its maximum value. Do not include the amount of alcohol added in the operation where only alcohol is added to the reaction vessel after the point where it drops to .

For example, each divided addition amount of metallic magnesium is divided into five times as x1 (kg), x2 (kg), x3 (kg), x4 (kg), and x5 (kg), and added dividedly into a reaction vessel, At the time of the first divisional addition of metallic magnesium, y1 (m ³ ) of alcohol and x1 (kg) of metallic magnesium are added to the reaction vessel, a reaction accelerator is further added, the temperature is raised to the reaction temperature, and the reaction is performed. is started and reacted for a predetermined period of time, and at the time of the second divided addition, a mixture of y2 (m ³ ) of alcohol and x2 (kg) of metallic magnesium dispersed is added to the reaction vessel, and the reaction is continued. , After reacting for a predetermined time, at the time of the third divided addition, a mixture of x3 (kg) of metallic magnesium dispersed in y3 (m ³ ) of alcohol is added to the reaction vessel, and the reaction is continued to continue the reaction. After reacting for a period of time, at the time of the fourth divided addition, a mixture of y4 (m ³ ) of alcohol and x4 (kg) of metallic magnesium dispersed is added to the reaction vessel, the reaction is continued, and the reaction is allowed to proceed for a predetermined period of time. After that, at the time of the fifth divided addition, a mixture of x5 (kg) of metallic magnesium dispersed in y5 (m ³ ) of alcohol was added to the reaction vessel, and the reaction was continued to react the metallic magnesium with the alcohol. If done, the A value is "x1/y1" and the B value is "(x1+x2+x3+x4+x5)/(y1+y2+y3+y4+y5)".

Further, for example, the amounts of metal magnesium to be added separately are divided into 5 times and added to the reaction vessel as x1 (kg), x2 (kg), x3 (kg), x4 (kg), and x5 (kg). Then, at the time of the first divisional addition of metallic magnesium, y1 (m ³ ) of alcohol and x1 (kg) of metallic magnesium are added to the reaction vessel, a reaction accelerator is further added, and the temperature is raised to the reaction temperature. , After starting the reaction and reacting for a predetermined time, at the time of the second divided addition, a mixture of x2 (kg) of metal magnesium dispersed in y2 (m ³ ) of alcohol is added to the reaction vessel, and the reaction is performed. After reacting for a predetermined time, a mixture of y3 (m ³ ) of alcohol and x3 (kg) of metal magnesium dispersed in alcohol is added to the reaction vessel at the time of the third divided addition, and the reaction is continued, After reacting for a predetermined time, only alcohol of y4 (m ³ ) was added to the reaction vessel, the reaction was continued, and after reacting for a predetermined time, y5 (m ³ ) in which x4 (kg) of metallic magnesium is dispersed is added, and the reaction is continued. After reacting for a predetermined time, y6 (m ³ ) of alcohol is added to the reaction vessel at the time of the fifth divided addition. To, when a mixture in which x5 (kg) of metallic magnesium is dispersed is added, the reaction is continued, and the reaction between metallic magnesium and alcohol is performed, the A value is "x1/y1", and the B value is "(x1+x2+x3+x4+x5)/(y1+y2+y3+y4+y5+y6)".

Further, for example, the amounts of metal magnesium to be added separately are divided into 5 times and added to the reaction vessel as x1 (kg), x2 (kg), x3 (kg), x4 (kg), and x5 (kg). Then, at the time of the first divisional addition of metallic magnesium, y1 (m ³ ) of alcohol and x1 (kg) of metallic magnesium are added to the reaction vessel, a reaction accelerator is further added, and the temperature is raised to the reaction temperature. , After starting the reaction and reacting for a predetermined time, at the time of the second divided addition, a mixture of x2 (kg) of metal magnesium dispersed in y2 (m ³ ) of alcohol is added to the reaction vessel, and the reaction is performed. After reacting for a predetermined time, a mixture of y3 (m ³ ) of alcohol and x3 (kg) of metal magnesium dispersed in alcohol is added to the reaction vessel at the time of the third divided addition, and the reaction is continued, After reacting for a predetermined time, at the time of the fourth divided addition, a mixture of x4 (kg) of metal magnesium dispersed in y4 (m ³ ) alcohol is added to the reaction vessel, the reaction is continued, and the reaction is continued for a predetermined time. After the reaction, at the time of the fifth divided addition, a mixture of x5 (kg) of metal magnesium dispersed in y5 (m ³ ) of alcohol is added to the reaction vessel, the reaction is continued, and after the fifth divided addition, Only y6 (m ³ ) of alcohol is added to the reaction vessel after the rate S (liters/minute) of hydrogen produced by the reaction has increased to its maximum value and has decreased to 45% of said maximum value. Then, when the reaction solution is continuously stirred to react metal magnesium with alcohol, the A value is "x1/y1" and the B value is "(x1+x2+x3+x4+x5)/(y1+y2+y3+y4+y5)". In other words, after the final addition of metallic magnesium, the rate of hydrogen generated by the reaction S (liters/minute) increased to its maximum value, and after it decreased to 45% of the maximum value, only alcohol was added to the reaction vessel. The amount of alcohol added in the operation of adding is "After the generation rate S (liters/minute) of hydrogen generated by the reaction after the operation of adding metallic magnesium from the beginning to the end increases to its maximum value, 45 of the maximum value %, not included in the total amount of alcohol added to the reaction vessel.

In the method for producing dialkoxymagnesium of the present invention, the ratio of B value to A value (B value/A value) is 2.10 to 8.50, preferably 2.50 to 8.50, particularly preferably 2.50 to 8.50. 50 to 8.00. When the ratio of the B value to the A value (B value/A value) is within the above range, dialkoxymagnesium with a narrow particle size distribution, a small BD, and particles that are difficult to break can be obtained. On the other hand, if the ratio of the B value to the A value (B value/A value) is less than the above range, there will be a lot of aggregates and fine particles adhering to the particle surface, and if it exceeds the above range, coarse particles will easily form particle size distribution. becomes wider.

In the method for producing dialkoxymagnesium of the present invention, the A value is preferably 5.0 to 50.0, particularly preferably 5.0 to 45.0, and more preferably 8.0 to 40.0. When the A value is within the above range, the effect of obtaining dialkoxymagnesium having a narrow particle size distribution, a high BD, and particles that are difficult to break is enhanced.

In the method for producing dialkoxymagnesium of the present invention, the B value is preferably 100.0 or less, more preferably 20.0 to 80.0, and particularly preferably 40.0 to 70.0. When the B value is within the above range, the effect of obtaining dialkoxymagnesium having a narrow particle size distribution, a high BD, and particles that are difficult to break is enhanced.

The reaction temperature in the method for producing dialkoxymagnesium of the present invention is not particularly limited as long as it is equal to or lower than the boiling point of the raw material mixture, preferably 30 to 100° C., particularly preferably 50 to 90° C., and the reaction time is The reaction time is preferably 0.5 to 15 hours, particularly preferably 1 to 10 hours, and the reaction atmosphere is an inert gas atmosphere.

After performing the method for producing dialkoxymagnesium of the present invention, the obtained dialkoxymagnesium is dried by a method such as heat drying, airflow drying, or vacuum drying, or washed with an inert hydrocarbon compound. removes the alcohol from the dialkoxymagnesium.

In the method for producing dialkoxymagnesium of the present invention, a halogen is used as the reaction accelerator, preferably _I2 is used, and the ratio of the B value to the A value is set to a specific range, preferably the A value is further adjusted. Mg that affects the reaction by adjusting the ratio of solid content and liquid content in the reaction system from the beginning of the reaction to the end point of the reaction by setting the B value to a specific range, more preferably further to a specific range, By controlling the component balance of the alcohol and the reaction accelerator, it is possible to obtain dialkoxymagnesium that satisfies all of the characteristics of a narrow particle size distribution, a high BD, and a particle that is difficult to break.

BD of dialkoxymagnesium obtained by the method for producing dialkoxymagnesium of the present invention is 0.10 to 0.60 g/mL, preferably 0.20 to 0.50 g/mL, particularly preferably 0.25 to 0 .45 g/mL. When the BD of the dialkoxymagnesium is within the above range, it is possible to maintain an appropriate porosity during catalysis, facilitate sedimentation, and increase the yield. Further, when olefin polymerization is carried out using this solid catalyst component, a polymer having a high BD is obtained. Furthermore, when it is used for copolymerization, since it maintains a porosity that can hold the rubber component inside the particles, the polymer is not sticky and fluidity can be ensured, and the polymer weight per unit volume is large. Become.

Particle size distribution index (SPAN) of dialkoxymagnesium obtained by the method for producing dialkoxymagnesium of the present invention:
SPAN = ( _D90 - _D10 )/ _D50
is preferably 2.0 or less, more preferably 1.5 or less, and particularly preferably 1.0 or less. Since the particle size distribution index (SPAN) of the dialkoxymagnesium is within the above range, when the dialkoxymagnesium is used as a carrier raw material for a solid catalyst component for olefin polymerization, the content of fine particles in the resulting solid catalyst component is reduced. and the resulting polymer has fewer fine particles. In the present invention, D ₁₀ , D ₅₀ , and D ₉₀ are cumulative volume fractions in the particle size distribution measured by a laser diffraction particle size distribution analyzer (MICROTRAC HRA Model No. 9320-X100, manufactured by Nikkiso Co., Ltd.). indicates the particle size (μm) corresponding to 10%, 50% and 90%, respectively. The above D ₁₀ , D ₅₀ and D ₉₀ are values obtained by dispersing dialkoxymagnesium in a dispersion medium such as ethanol when measuring with a laser diffraction particle size distribution analyzer.

The average particle diameter (D ₅₀ ) of dialkoxymagnesium obtained by the method for producing dialkoxymagnesium of the present invention is preferably 5 to 100 μm, more preferably 10 to 80 μm, and particularly preferably 15 to 70 μm. Since the average particle diameter (D ₅₀ ) of the dialkoxymagnesium is within the above range, when the dialkoxymagnesium is used as a carrier raw material for a solid catalyst component for olefin polymerization, the content of fine particles in the solid catalyst component obtained is and the resulting polymer has fewer fine particles.

The dialkoxymagnesium obtained by the method for producing dialkoxymagnesium of the present invention is hard to break when a load is applied. The brittleness of dialkoxymagnesium can be grasped, for example, by the brittleness measurement shown below. As a measuring device, a laser diffraction particle size distribution measuring device (Malvern Co., Ltd., Mastersizer 3000) or the like can be used. When using a laser diffraction particle size distribution measuring device, the dialkoxymagnesium is dispersed in an air stream, and the particle size distribution is measured under two conditions of a dispersion pressure of 1.5 bar and 3.0 bar to determine the existence ratio of fine particles. Fragility of dialkoxymagnesium is determined from the difference between the existence ratio of fine particles when the particle size distribution is measured under the condition of 0 bar and the existence ratio of fine particles when the particle size distribution is measured under the condition of dispersion pressure of 1.5 bar. can be confirmed. In the present invention, using a laser diffraction particle size distribution analyzer (Malvern Co., Mastersizer 3000), dialkoxymagnesium is dispersed in an air flow with a dispersion pressure of 3.0 bar, and the particle size distribution is measured to 11.0 μm. The abundance ratio (% by volume) of the following particles, and the abundance ratio (% by volume) of particles of 11.0 μm or less when the particle size distribution is measured by dispersing the dialkoxymagnesium in an air flow with a dispersion pressure of 1.5 bar, was used as a judgment index for fragility.

The dialkoxymagnesium obtained by the method for producing dialkoxymagnesium of the present invention preferably does not contain alcohol, but an alcohol content of 2% by mass or less is acceptable.

The purity of dialkoxymagnesium obtained by the method for producing dialkoxymagnesium of the present invention is 99.0% by mass or more, more preferably 99.0 to 100% by mass, and particularly preferably 99.1 to 99.9. % by mass. In the present invention, the purity of the dialkoxymagnesium means the purity of the dialkoxymagnesium after the solvent is removed, and the halogen content in the dialkoxymagnesium after the solvent is removed. It is a value calculated from the reaction accelerator content by the following formula.
Dialkoxymagnesium purity (mass%) = 100 - reaction accelerator content (mass%)

The dialkoxymagnesium obtained by the method for producing dialkoxymagnesium of the present invention is suitably used as a raw material for producing a solid catalyst component for olefin polymerization.

The method for producing the solid catalyst component for polymerization of olefins using the dialkoxymagnesium obtained by the method for producing dialkoxymagnesium of the present invention as a raw material is not particularly limited and may be appropriately selected.

Examples of the solid catalyst component for olefin polymerization and the method for producing the same include the following solid catalyst component for olefin polymerization and the method for producing the same.

The solid catalyst component for olefin polymerization of the present invention comprises dialkoxymagnesium (a) obtained by the method for producing dialkoxymagnesium of the present invention, a titanium halogen compound (b), and an electron donating compound (c). A solid catalyst component for olefin polymerization, characterized in that it is obtained by contacting with

Dialkoxymagnesium (a) according to the solid catalyst component for olefin polymerization of the present invention is dialkoxymagnesium obtained by the method for producing dialkoxymagnesium of the present invention. The details of the method for producing dialkoxymagnesium of the present invention are as described above.

As the titanium halogen compound (b) constituting the solid catalyst component for olefin polymerization of the present invention, one or more selected from known compounds can be mentioned, preferably a tetravalent titanium halogen compound, more preferably titanium tetrachloride.

As the electron-donating compound (c) constituting the solid catalyst component for olefin polymerization of the present invention, one or more selected from known substances can be mentioned, and an organic compound having an oxygen atom or a nitrogen atom is preferable.

The electron donating compound (c) is preferably one or more selected from succinate, maleate, cyclohexene carboxylate, ether carboxylate, dicarbonate and ether carbonate.

In the solid catalyst component for olefin polymerization of the present invention, the contents of titanium atoms, magnesium atoms, halogen atoms and electron-donating compounds are not particularly defined.

In the solid catalyst component for olefin polymerization of the present invention, the content of titanium atoms is preferably 0.5 to 8.0% by mass, more preferably 1.0 to 6.0% by mass, More preferably, it is 1.0 to 4.0% by mass.

In the solid catalyst component for olefin polymerization of the present invention, the content of magnesium atoms is preferably 10 to 70% by mass, more preferably 10 to 50% by mass, and 15 to 40% by mass. is more preferable, and 15 to 25% by mass is even more preferable.

In the solid catalyst component for olefin polymerization of the present invention, the content of halogen atoms is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and 40 to 80% by mass. is more preferable, and 45 to 75% by mass is even more preferable.

In the solid catalyst component for olefin polymerization of the present invention, the total content of the electron donating compound (c) is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass. It is preferably 2 to 20% by mass, and more preferably 2 to 20% by mass.

In order for the solid catalyst component for olefin polymerization of the present invention to exhibit its overall performance in a well-balanced manner, the titanium content is 1 to 4% by mass, the magnesium content is 15 to 25% by mass, and the halogen atom content is It is desirable that the content of the electron-donating compound (c) is 45 to 75% by mass and 2 to 20% by mass.

As a method for producing the solid catalyst component for olefin polymerization of the present invention, an alkoxymagnesium (a), a titanium halogen compound (b) and an electron donating compound (c) are mixed with an inert organic solvent having a boiling point of 50 to 150°C. A method of contacting in the presence of (d) can be mentioned.

Examples of the inert organic solvent (d) having a boiling point of 50 to 150° C. include one or more selected from toluene, xylene, ethylbenzene, heptane, octane, decane, and the like. As the inert organic solvent (d) having a boiling point of 50 to 150° C., aromatic hydrocarbon compounds and aliphatic hydrocarbon compounds are generally used. Inert organic solvents other than aromatic hydrocarbons and saturated hydrocarbons, if present, may also be used.

Further, when producing the solid catalyst component for olefin polymerization of the present invention, polysiloxane may be added to the reaction system. As the polysiloxane, conventionally known ones are appropriately selected, but one or more selected from decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable, and decamethylcyclopentasiloxane is more preferable.

The details of the method for preparing the solid catalyst component for olefin polymerization of the present invention are the same as the methods for preparing conventionally known solid catalyst components for olefin polymerization.

As described above, the solid catalyst component for olefin polymerization of the present invention comprises dialkoxymagnesium (a) obtained by the method for producing dialkoxymagnesium of the present invention, a titanium halogen compound (b), an electron It is obtained by contacting and reacting with the donor compound (c).

According to the present invention, it is possible to provide a solid catalyst component for olefin polymerization that has a narrow particle size distribution, a small amount of fine powder, a high BD, and is resistant to breakage.

The olefin polymerization catalyst according to the present invention is obtained by contacting (A) the solid catalyst component for olefin polymerization of the present invention, (B) an organoaluminum compound and (C) an external electron donating compound. An olefin polymerization catalyst characterized by:

The (A) solid catalyst component for olefin polymerization according to the present invention is as described above.

The olefin polymerization catalyst of the present invention contains (B) an organoaluminum compound. (B) The organoaluminum compound is not particularly limited as long as it can be used as an olefin polymerization catalyst.

In the olefin polymerization catalyst of the present invention, the (B) organoaluminum compound has the following general formula (2):
R ² _p AlQ _3-p (2)
(In the formula, R ² represents an alkyl group having 1 ^to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0<p≦3. ² may be the same or different, and when there are a plurality of Qs, each Q may be the same or different.) is preferred.

The organoaluminum compound represented by the general formula (2) is not particularly limited, but R ² includes one or more selected from ethyl group and isobutyl group, and Q includes hydrogen atom, chlorine atom and One or more selected from bromine atoms can be mentioned, and p is preferably 2, 2.5 or 3, particularly preferably 3.

Specific examples of such organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum and triisobutylaluminum; alkylaluminum halides such as diethylaluminum chloride and diethylaluminum bromide; One or more selected from aluminum hydride and the like can be mentioned, and among them, one or more selected from alkylaluminum halide such as diethylaluminum chloride, or trialkylaluminum such as triethylaluminum, tri-n-butylaluminum and triisobutylaluminum is preferable. , triethylaluminum and triisobutylaluminum are more preferable.

The olefin polymerization catalyst of the present invention contains an external electron donating compound (C). The external electron-donating compound (C) is not particularly limited as long as it can be used as an olefin polymerization catalyst. In the olefin polymerization catalyst of the present invention, the external electron donating compound (C) is preferably a known external electron donating compound containing an oxygen atom or a nitrogen atom.

In the olefin polymerization catalyst of the present invention, the external electron donating compound (C) has the following general formula (3):
R ³ _q Si(OR ⁴ ) _4-q (3)
(wherein R ³ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, a carbon represents an aromatic hydrocarbon group of 6 to 15 carbon atoms or an aromatic hydrocarbon group of 6 to 15 carbon atoms having a substituent, and when a plurality of R ³ are present, the plurality of R ³ may be the same or different; R ⁴ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent; is an aromatic hydrocarbon group having 7 to 12 carbon atoms, and when a plurality of R ⁴ are present, the plurality of R ⁴ may be the same or different, and q is an integer of 0≦q≦3. ) and the general formula (4):
(R ⁵ R ⁶ N) _s SiR ⁷ _4-s (4)
(wherein R ⁵ and R ⁶ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ⁵ and R ⁶ may be the same or different, and may be combined to form a ring, and R ⁵ R ⁶ N group are present, the plurality of R ⁵ R ⁶ N groups may be the same or different, and ^{R 7} is an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, a vinyloxy group, an alkenyloxy group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyloxy group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, represents an aryloxy group having 6 to 20 carbon atoms, and when a plurality of R ⁷ are present, the plurality of R ⁷ may be the same or different, and s is an integer of 1 to 3.) One or more selected from compounds can be mentioned.

Examples of the organosilicon compound represented by the general formula (3) or the aminosilane compound represented by the general formula (4) include phenylalkoxysilanes, alkylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes, alkyl(cycloalkyl) Alkoxysilane, (alkylamino)alkoxysilane, alkyl(alkylamino)alkoxysilane, cycloalkyl(alkylamino)alkoxysilane, tetraalkoxysilane, tetrakis(alkylamino)silane, alkyltris(alkylamino)silane, dialkylbis(alkyl amino)silane, trialkyl(alkylamino)silane, and the like.

Specific examples of the organosilicon compound represented by the general formula (3) or the aminosilane compound represented by the general formula (4) include n-propyltriethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyl triethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, bis(2-ethylhexyl)dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, di Cyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, tetrabutoxysilane, bis(ethylamino)methylethylsilane, bis(ethylamino)t-butylmethylsilane, bis(ethylamino) ) dicyclohexylsilane, dicyclopentylbis(ethylamino)silane, bis(methylamino)(methylcyclopentylamino)methylsilane, diethylaminotriethoxysilane, bis(cyclohexylamino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, bis One or more selected from (perhydroquinolino)dimethoxysilane, ethyl(isoquinolino)dimethoxysilane, etc., and among them, n-propyltriethoxysilane, phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane. silane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis(ethylamino)silane, At least one selected from bis(ethylamino)dicyclohexylsilane, dicyclopentylbis(ethylamino)silane, bis(perhydroisoquinolino)dimethoxysilane, diethylaminotriethoxysilane and the like is preferred.

The olefin polymerization catalyst of the present invention contains (A) the solid catalyst component for olefin polymerization of the present invention, (B) an organoaluminum compound represented by the general formula (2), and (C) an external electron donating compound. The ratio is arbitrarily selected within the range in which the effects of the present invention can be obtained, and is not particularly limited. The amount of the organoaluminum compound represented by 2) is preferably 1 to 2000 mol, more preferably 50 to 1000 mol. Further, (B) the external electron donating compound (C) is preferably 0.002 to 10 mol, preferably 0.01 to 2 mol, per 1 mol of the organoaluminum compound represented by the general formula (2). more preferably 0.01 to 0.5 mol.

The method for producing the olefin polymerization catalyst of the present invention is not particularly limited. ) A method of producing an olefin polymerization catalyst by contacting an external electron-donating compound by a known method.
Although the order of contacting each of the above components is arbitrary, the following contact order can be exemplified, for example.
(i) (A) Solid catalyst component for olefin polymerization of the present invention → (C) external electron donating compound → (B) organoaluminum compound represented by general formula (2) (ii) (B) general formula ( Organoaluminum compound represented by 2) → (C) external electron donating compound → (A) solid catalyst component for olefin polymerization of the present invention (iii) (C) external electron donating compound → (A) of the present invention Solid catalyst component for olefin polymerization → (B) organoaluminum compound represented by general formula (2) (iv) (C) external electron donating compound → (B) organoaluminum compound represented by general formula (2) →(A) Solid catalyst component for polymerization of olefins of the present invention Among the contact examples (i) to (iv), the contact example (ii) is preferable.
In the above contact examples (i) to (iv), "→" means the order of contact. The organoaluminum compound represented by the formula (C) external electron-donating compound is obtained by adding (B) an organoaluminum compound represented by the general formula (2) to (A) the solid catalyst component for olefin polymerization of the present invention. (C) the external electron donating compound is added and contacted.

The catalyst for olefin polymerization of the present invention comprises (A) the solid catalyst component for olefin polymerization of the present invention, (B) an organoaluminum compound represented by general formula (2), and (C) an external electron donating compound, The contact may be made in the absence of olefins, or the contact may be made in the presence of olefins (within the polymerization system).

According to the present invention, it is possible to provide an olefin polymerization catalyst that has a narrow particle size distribution, a small amount of fine powder, a high BD, and is resistant to breakage.

The method for producing an olefin polymer of the present invention is characterized by polymerizing olefins in the presence of the olefin polymerization catalyst of the present invention.

In the method for producing an olefin polymer of the present invention, the polymerization of olefins may be homopolymerization or copolymerization.

In the method for producing an olefin polymer of the present invention, examples of olefins include one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like. , propylene or 1-butene are preferred, with propylene being more preferred.

When propylene is polymerized, it may be copolymerized with other olefins, preferably by block copolymerization of propylene and other α-olefins. A block copolymer obtained by block copolymerization is a polymer containing segments in which the composition of two or more monomers changes continuously. It refers to a form in which two or more types of polymer chains (segments) with different primary structures such as sex are connected in one molecular chain. The olefins to be copolymerized are preferably α-olefins having 2 to 20 carbon atoms (excluding propylene having 3 carbon atoms). Specifically, ethylene, 1-butene, 1-pentene, 4- Examples include methyl-1-pentene and vinylcyclohexane, and these olefins may be used in combination of one or more. Ethylene and 1-butene are particularly preferred.

In the method for producing an olefin polymer of the present invention, olefins can be polymerized in the presence or absence of an organic solvent. In addition, in the method for producing an olefin polymer of the present invention, olefins to be polymerized can be used in either gaseous or liquid state.

Regarding the polymerization of olefins, for example, in a reactor such as an autoclave, olefins are introduced in the presence of the catalyst for olefin polymerization of the present invention, and the olefins are polymerized under heating and pressurized conditions. be able to.

In the method for producing an olefin polymer of the present invention, the polymerization temperature is usually 200° C. or lower, preferably 100° C. or lower, and more preferably 60 to 100° C. from the viewpoint of improving activity and stereoregularity. 70 to 90°C is more preferred. In the method for producing an olefin polymer of the present invention, the polymerization pressure is preferably 10 MPa or less, more preferably 5 MPa or less. Moreover, either a continuous polymerization method or a batch polymerization method is possible. Furthermore, the polymerization reaction may be carried out in one step or in two or more steps.

In the method for producing an olefin polymer of the present invention, when olefins are polymerized (hereinafter referred to as main polymerization as appropriate), the constituent components of the olefin polymerization catalyst of the present invention are added to the olefins to be polymerized. Preliminary polymerization (hereinafter referred to as prepolymerization as appropriate) may be performed by contacting a part or all of the.

In prepolymerization, the constituent components of the catalyst for polymerization of olefins of the present invention and the olefins may be brought into contact in any order. After charging and then contacting with the solid catalyst component for polymerization of olefins of the present invention, it is preferable to contact with one or more olefins such as propylene. Alternatively, the organoaluminum compound is first charged into a prepolymerization system set in an inert gas atmosphere or an olefin gas atmosphere, then brought into contact with an external electron-donating compound, and further brought into contact with the solid catalyst component for olefin polymerization of the present invention. Then, it is preferable to contact with one or more olefins such as propylene. In prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used, and the prepolymerization conditions are also the same as the above polymerization conditions.

By carrying out the above prepolymerization, the catalyst activity is improved, and the stereoregularity, particle properties, etc. of the obtained polymer can be further improved.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the olefin polymer which can manufacture the polymer with narrow particle size distribution and high BD under high polymerization activity can be provided. Further, in the present invention, since the solid catalyst component for olefin polymerization whose particles are hard to break is used, the amount of fine powder in the polymer obtained by polymerization is also reduced.
The method for producing an olefin polymer according to the present invention is particularly applied to a process for producing polyolefin by a gas phase method.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but these are merely examples and are not intended to limit the present invention.

(Example 1)
2,000 mg of metallic magnesium powder (average particle size: 132.6 μm), anhydrous ethanol were placed in a 1-liter four-necked flask equipped with an integrating gas meter, a dropping funnel, a stirrer, and a reflux condenser, and filled with nitrogen gas. 95.0 mL (60 g) and 0.645 g (2.54 mmol) of iodine (I ₂ ) were charged (first portionwise addition) and heated in an oil bath to the reflux temperature of ethanol and maintained at reflux. At this time, the A value is 21.1.
Next, after continuing to stir under reflux for 5 minutes, a mixture of metallic magnesium powder and ethanol was added (second divided addition), and then the operation was carried out in the same manner as the second divided addition. Repeated five times (3-7 portion additions) to drive the reaction to completion. The amount of metallic magnesium powder added in the second to seventh divided additions was calculated by equally dividing the total amount of metallic magnesium powder added in the second and subsequent times shown in Table 1 (960 mg/time). The amount of ethanol added in the second to seventh divided additions was also calculated by equally dividing the total amount of ethanol added in the second and subsequent times (7.0 mL/time) in the same manner as in the metal magnesium powder.
Then, the reaction solution was dried with a rotary evaporator to obtain 32.89 mg of powdery diethoxymagnesium.
At this time, the B value is 56.6, and the B value/A value is 2.68.
Analysis of the obtained diethoxymagnesium revealed that the halogen content was 3.44% by mass. Also, BD, SPAN, and fragility measurements of the resulting diethoxymagnesium were performed. Table 1 shows the results.

<Analysis of BD>
BD (bulk specific gravity) of the obtained dialkoxymagnesium was measured according to JIS K6721.

<Analysis of SPAN>
Using a laser diffraction particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., MICROTRAC HRA 9320-X100), dialkoxymagnesium is dispersed in absolute ethanol, automatic measurement is performed twice, the particle size distribution is measured, and the cumulative volume fraction is measured. The particle diameter (D ₁₀ ) at a rate of 10%, the particle diameter (D ₅₀ ) at an accumulated volume fraction of 50%, and the particle diameter (D ₉₀ ) at an accumulated volume fraction of 90% are obtained, and the average values are D ₁₀ and D ₅₀ and _D90 . Then, from the values of D ₁₀ , D ₅₀ and D ₉₀ thus obtained, SPAN was calculated according to the following formula.
SPAN = ( _D90 - _D10 )/ _D50

<Purity of dialkoxymagnesium>
The purity (mass%) of the obtained dialkoxymagnesium is measured by an automatic titrator automatic titrator (manufactured by Mitsubishi Chemical Analytic Tech, model GT-200), and the halogen in the dialkoxymagnesium after removing the solvent. From the content (% by mass), the content (% by mass) of the compound used as the reaction accelerator in the dialkoxymagnesium was obtained and calculated by the following formula.
Dialkoxymagnesium purity (mass%) = 100 - reaction accelerator content (mass%)

<Breakability measurement>
Using a laser diffraction particle size distribution analyzer (Malvern, Mastersizer 3000), the dialkoxymagnesium was dispersed in an air flow with a dispersion pressure of 1.5 bar, and the particle size distribution was measured by automatic measurement twice. , the existence ratio (volume %) of particles of 11.0 μm or less was determined. In addition, the dialkoxymagnesium was dispersed in an air stream with a dispersion pressure of 3.0 bar, and the particle size distribution was measured by automatic measurement twice to determine the existence ratio (volume %) of particles of 11.0 μm or less. The existence ratio X volume % of particles of 11.0 μm or less when dispersed in an air flow with a dispersion pressure of 3.0 bar, and the abundance ratio Y of particles with a diameter of 11.0 μm or less when dispersed in an air flow with a dispersion pressure of 1.5 bar. The difference from volume % was calculated.

(Examples 2-4 and Comparative Examples 1-2)
The same procedure as in Example 1 was carried out, except that the amounts of metal magnesium and ethanol added and the number of divided additions were as shown in Table 1. Table 1 shows the results.

(Comparative Example 3)
As a reaction accelerator, instead of 0.645 g of iodine (I ₂ ), 0.15 g (2.54 mmol) of magnesium chloride (specific surface area: 14 m ² /g) was used, and the amount of metal magnesium and ethanol added and the number of divided additions was carried out in the same manner as in Example 1, except that the was performed as shown in Table 1. Table 1 shows the results.

(Comparative Example 4)
500 mg of metallic magnesium powder (average particle size: 128.8 μm), anhydrous ethanol were placed in a 1-liter four-necked flask equipped with an integrating gas meter, dropping funnel, stirrer, and reflux condenser and filled with nitrogen gas. 111.0 mL (g) and 0.297 g (1.17 mmol) of iodine (I ₂ ) were charged (first portionwise addition) and heated in an oil bath to the reflux temperature of ethanol and maintained at reflux. At this time, the A value is 4.5.
Next, after continuing to stir under reflux for 5 minutes, a mixture of metallic magnesium powder and ethanol was added (second divided addition), and then the operation was carried out in the same manner as the second divided addition. Repeated five times (3-7 portion additions) to drive the reaction to completion. The amount of metallic magnesium powder added in the second to seventh divided additions was calculated by equally dividing the total amount of metallic magnesium powder added in the second and subsequent times shown in Table 1 (1210 mg/time). The amount of ethanol added in the 2nd to 7th divided additions was also calculated by equally dividing the total added amount of ethanol from the 2nd time onward (13.8 mL/time, 14.0 mL only for the 7th time) in the same way as for the metal magnesium powder.
Then, the reaction solution was dried with a rotary evaporator to obtain 30.7 g of powdery diethoxymagnesium.
At this time, the B value is 40.0, and the B value/A value is 8.89.
Analysis of the resulting diethoxymagnesium revealed that the halogen content was 3.24% by mass. Also, BD, SPAN, and fragility measurements of the resulting diethoxymagnesium were performed. Table 1 shows the results.

(Comparative Example 5)
The same procedure as in Comparative Example 4 was carried out, except that the amounts of metallic magnesium and ethanol added were as shown in Table 1. Table 1 shows the results.

１）分散圧３．０ｂａｒの気流に分散させたときの１１．０μｍ以下の粒子の存在割合Ｘ体積％と、分散圧１．５ｂａｒの気流に分散させたときの１１．０μｍ以下の粒子の存在割合Ｙ体積％との差（Ｘ－Ｙ）

1) Existence ratio X volume % of particles of 11.0 µm or less when dispersed in an air stream with a dispersion pressure of 3.0 bar, and existence of particles of 11.0 µm or less when dispersed in an air stream with a dispersion pressure of 1.5 bar Difference from the ratio Y volume % (XY)

(Example 5)
<Preparation of solid catalyst component for olefin polymerization>
30 ml of titanium tetrachloride and 20 ml of toluene were charged into a 500 ml capacity round-bottomed flask fully purged with nitrogen gas and equipped with a stirrer to form a mixed solution. Then, a suspension formed using 10 g of diethoxymagnesium obtained in Example 1 above, 50 ml of toluene and 3.3 ml (12.5 mmol) of di-n-butyl phthalate was heated to a liquid temperature of 10°C. It was added to the retained mixed solution.
After that, the liquid temperature was raised from 10° C. to 90° C., and the mixture was reacted at 90° C. for 2 hours while stirring.
After completion of the reaction, the obtained solid product was washed four 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 reacted with stirring for 2 hours. After completion of the reaction, the solid catalyst component for olefin polymerization (A-1) was obtained by washing 10 times with 100 ml of n-heptane at 40°C.
The solid catalyst component (A-1) contained 14.2% by mass of a phthalate diester as an internal electron donating compound. Also, when the titanium content in this solid catalyst component was measured, it was 2.2% by weight.
<Formation of Olefin Polymerization Catalyst and Propylene Polymerization>
1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane, and the above solid catalyst component (A-1) were placed in an autoclave with an internal volume of 2.0 liters and equipped with a stirrer, which had been completely purged with nitrogen gas, in terms of titanium atoms. was charged at 0.0026 mmol to form a catalyst for olefin polymerization.
Next, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged into the autoclave, prepolymerized at 20°C for 5 minutes, heated to 70°C, and polymerized at 70°C for 1 hour. A propylene polymer was obtained by carrying out. Table 3 shows the polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer.
<Average Particle Size, Particle Size Distribution Index, and Amount of Fine Powder with a Particle Size of Less Than 75 μm>
The average particle size, particle size distribution index, and amount of fine powder with a particle size of less than 75 μm of the obtained polymer were measured using a digital image analysis type particle size distribution measuring device (Camsizer, manufactured by Horiba, Ltd.) under the following measurement conditions. Automatic measurement of the volume-based integrated particle size distribution of the polymer was performed.
(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: 40mm
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 Martin diameter measured n times per particle SPHT (sphericity) fitting: 1
Class upper limit: Select 50 points in the range of 32 μm to 4000 μm on a logarithmic scale

(Comparative Example 6)
In the same manner as in Example 1, except that 10 g of diethoxymagnesium obtained in Comparative Example 1 was used instead of 10 g of diethoxymagnesium obtained in Example 1, the solid catalyst component for olefin polymerization was prepared and olefin was polymerized. A catalyst was formed, propylene was polymerized, and the physical properties of the resulting polymer were evaluated. Table 2 shows the polymerization activity per 1 g of the solid catalyst component and the physical properties of the obtained polymer.

Claims (6)

A dialkoxymagnesium production method for obtaining dialkoxymagnesium by reacting metallic magnesium with an alcohol in the presence of a reaction accelerator,
using iodine (I ₂ ) as the reaction accelerator;
that the alcohol is ethanol;
adding the metallic magnesium to the reaction vessel in multiple batches;
The molar ratio (iodine/magnesium metal) of the total amount (mol) of iodine (I ₂ ) added as the reaction accelerator to the total amount (mol) of magnesium metal is 0.001 to 0.008. ,
A value is defined as the amount of metallic magnesium in the reaction vessel at the start of the reaction (kg)/the amount of alcohol in the reaction vessel at the start of the reaction (m ³ ). After the total amount of metallic magnesium added to the container (kg)/the generation rate S (liters/minute) of hydrogen produced by the reaction after the operation of adding metallic magnesium from the beginning to the end increases to its maximum value, 45 of said maximum value %, the A value is 5.0 to 50.0, where the value of the total amount of alcohol (m ³ ) added to the reaction vessel is defined as the B value, and the B value is 40.0 to 70.0 and the ratio of the B value to the A value (B value/A value) is 2.10 to 8.50,
A method for producing dialkoxymagnesium, characterized by: The method for producing dialkoxymagnesium according to claim 1 is performed to obtain dialkoxymagnesium, and then the obtained dialkoxymagnesium (a), the titanium halogen compound (b), and the electron donating compound (c) are combined. A method for producing a solid catalyst component for polymerization of olefins, characterized by obtaining a solid catalyst component for polymerization of olefins by contacting the component. (A) performing the method for producing a solid catalyst component for polymerization of olefins according to claim 2 to obtain a solid catalyst component for polymerization of olefins; and (C) a method for producing an olefin polymerization catalyst, which comprises bringing an external electron-donating compound into mutual contact to obtain an olefin polymerization catalyst. The (B) organoaluminum compound has the following general formula (2):
R ² _p AlQ _3-p (2)
(In the formula, R ² represents an alkyl group having 1 ^to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0<p≦3. ² may be the same or different, and when there are multiple Qs, each Q may be the same or different.)
4. The method for producing an olefin polymerization catalyst according to claim 3, wherein the organoaluminum compound is represented by: The (C) external electron donating compound has the following general formula (3):
R ³ _q Si(OR ⁴ ) _4-q (3)
(wherein R ³ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, a carbon represents an aromatic hydrocarbon group of 6 to 15 carbon atoms or an aromatic hydrocarbon group of 6 to 15 carbon atoms having a substituent, and when a plurality of R ³ are present, the plurality of R ³ may be the same or different; R ⁴ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituent; is an aromatic hydrocarbon group having 7 to 12 carbon atoms, and when a plurality of R ⁴ are present, the plurality of R ⁴ may be the same or different, and q is an integer of 0≦q≦3. )
and an organosilicon compound represented by the general formula (4):
(R ⁵ R ⁶ N) _s SiR ⁷ _4-s (4)
(wherein R ⁵ and R ⁶ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R ⁵ and R ⁶ may be the same or different, and may be combined to form a ring, and R ⁵ R ⁶ N group are present, the plurality of R ⁵ R ⁶ N groups may be the same or different, and ^{R 7} is an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms, a vinyloxy group, an alkenyloxy group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyloxy group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, represents an aryloxy group having 6 to 20 carbon atoms, and when a plurality of R ⁷ are present, the plurality of R ⁷ may be the same or different, and s is an integer of 1 to 3.)
5. The method for producing a catalyst for polymerization of olefins according to claim 3 or 4, characterized in that it is one or more selected from aminosilane compounds represented by: The method for producing an olefin polymerization catalyst according to any one of claims 3 to 5 is performed to obtain an olefin polymerization catalyst, and then olefins are polymerized in the presence of the obtained olefin polymerization catalyst. A method for producing an olefin polymer characterized by: