JP2019172775A - Olefin polymerization catalyst, method for producing olefin polymerization catalyst, and method for producing olefin polymer - Google Patents

Abstract

To provide an olefin polymerization catalyst that can effectively produce an olefin polymer having a narrow particle size distribution by significantly reducing the amounts of a fine powder and a coarse powder generated in the obtained olefin polymer.SOLUTION: Provided is an olefin polymerization catalyst, comprising a mixture of a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound, an organoaluminum compound and an inorganic oxide particle, and in which, characterized, the inorganic oxide particle has a number ratio of particles composed of primary particles of 50 to 100% and an average particle size of 1/100 or less of the average particle size of the solid catalyst component.SELECTED DRAWING: None

Description

  The present invention relates to an olefin polymerization catalyst, a method for producing an olefin polymerization catalyst, and a method for producing an olefin polymer.

  In the polymerization of olefins such as propylene, a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound as essential components is known, and the solid catalyst component, organoaluminum compound and organic Many methods for polymerizing or copolymerizing olefins in the presence of an olefin polymerization catalyst comprising a silicon compound have been proposed (see, for example, Patent Document 1).

JP-A-11-106434

In general, when the olefins are polymerized using the solid catalyst component for polymerization of highly active olefins as described above, the solid catalyst component itself generates a fine powder component and a fine powder component due to particle breakage during polymerization. The amount of fine powder increases, and the particle size distribution of the polymer produced also becomes broad.
When the amount of fine powder polymer increases, the continuation of the uniform reaction in the polymerization system is hindered, and not only does it cause a process failure such as blockage of the pipe during the transfer of the polymer, but also the particle size distribution of the resulting polymer is reduced. Since the processability of the olefin polymer is likely to be reduced by widening, an olefin polymerization catalyst that can suitably produce a polymer having a small amount of fine powder polymer and a uniform and narrow particle size distribution is provided. It came to be desired.

In order to obtain such an olefin polymerization catalyst, various studies have been made on the use of a substance other than a magnesium compound as a carrier for a solid catalyst component for olefin polymerization. For example, it is supported on a magnesium chloride / silicon dioxide composite carrier. A method for improving the particle shape of the resulting ethylene polymer by treating the solid catalyst component with a surfactant component and then subjecting it to ethylene polymerization is conceivable.
However, according to the study of the present inventors, when the solid catalyst component is treated with a surfactant component, the amount of finely divided ethylene polymer can be reduced, but when subjected to propylene polymerization, It turned out that the effect was difficult to obtain.

Further, for example, a solid component (component 1) of a Ziegler-type catalyst containing a titanium atom, a magnesium atom and a halogen atom as essential components, an inorganic oxide, carbonate, sulfate and the like having an average particle size smaller than that of the solid component The catalyst for olefin polymerization comprising a mixture with a compound selected from the above mixture (component 2) can clog the catalyst introduction tube during ethylene polymerization, polymer adhesion due to catalyst adhesion in the polymerization tank, generation of coarse particles, etc. It is possible to suppress it.
However, according to the study of the present inventor, it has been found that the effect of the above method on the amount of fine powder polymer produced during propylene polymerization is not clear, and it is difficult to obtain the same effect in propylene polymerization.

  Accordingly, the present invention provides an olefin polymerization catalyst that can significantly reduce the amount of fine powder and coarse powder generated in the resulting olefin polymer and can effectively produce an olefin polymer having a narrow particle size distribution. In addition, an object of the present invention is to provide a method for producing an olefin polymerization catalyst and a method for producing an olefin polymer.

  Under such circumstances, the present inventors have conducted intensive studies to solve the above problems, and as a result, a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound, an organic A catalyst for olefin polymerization comprising a mixture of an aluminum compound and inorganic oxide particles, wherein the inorganic oxide particles have a number ratio of primary particles of 50 to 100%, and the average particle size is the solid catalyst. It has been found that the above technical problem can be solved by an olefin polymerization catalyst having an average particle size of 1/100 or less of the component, and the present invention has been completed.

That is, the present invention
(1) A catalyst for olefin polymerization comprising a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound, an organoaluminum compound, and a mixture of inorganic oxide particles,
Olefin polymerization, wherein the inorganic oxide particles have a primary particle number ratio of 50 to 100% and an average particle size of 1/100 or less of the average particle size of the solid catalyst component. Catalyst.
(2) The catalyst for olefin polymerization according to (1) above, wherein the inorganic oxide particles have an average particle size of 200 nm or less and a true density of 2.1 g / cm ³ or more.
(3) The olefin polymerization catalyst according to (1) or (2) above, wherein the content of the inorganic oxide particles with respect to 100 parts by mass of the solid catalyst component is 2 parts by mass or more,
(4) The organoaluminum compound is represented by the following general formula (I):
R ¹ _p AlQ _3-p (I)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is a real number of 0 <p ≦ 3, each of R ¹ if R ¹ there are a plurality of May be the same or different, and when there are multiple Qs, each Q may be the same or different)
The catalyst for olefin polymerization according to any one of the above (1) to (3), which is represented by:
(5) The following general formula (II);
R ² _q Si (OR ³ ) _4-q (II)
(In the formula, R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a vinyl group, an allyl group, an aralkyl group, an alkylamino group having 1 to 12 carbon atoms, or carbon. In the case where a dialkylamino group having 1 to 12 and a plurality of R ² are present, each R ² may be the same or different, and R ³ is an alkyl or cycloalkyl group having 1 to 4 carbon atoms. , A phenyl group, a vinyl group, an allyl group, or an aralkyl group, and when a plurality of R ³ are present, each R ³ may be the same or different, and q is an integer of 0 ≦ q ≦ 3. )
An organosilicon compound selected from the following general formula (III):
(R ⁴ R ⁵ N) _r SiR ⁶ _4-r (III)
(In the formula, R ⁴ and R ⁵ are each a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or a cyclohexane having 3 to 20 carbon atoms. An alkyl group or an aryl group, which may be the same or different, and R ⁴ and R ⁵ may be bonded to each other to form a ring, and R ⁶ is a straight chain having 1 to 20 carbon atoms or 3 carbon atoms; 20 branched alkyl group, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group or an aryl group having 3 to 20 carbon atoms, if R ⁶ is plural, R ⁶ may be the same or different R is an integer from 1 to 3)
The olefin polymerization catalyst according to any one of (1) to (4) above, which comprises any one or more external electron donating compounds selected from the aminosilane compounds represented by:
(6) The number ratio of particles comprising a solid catalyst component containing magnesium atom, titanium atom, halogen atom and internal electron donating compound, organoaluminum compound and primary particles is 50 to 100%, and the average particle size is the solid A method for producing an olefin polymerization catalyst, comprising mixing inorganic oxide particles having an average particle diameter of 1/100 or less of a catalyst component,
And (7) A method for producing an olefin polymer, characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst according to any one of (1) to (5) above. It is.

  According to the present invention, there is provided an olefin polymerization catalyst capable of effectively producing an olefin polymer having a narrow particle size distribution by significantly reducing the amount of fine powder and coarse powder generated in the resulting olefin polymer. In addition, a method for producing an olefin polymerization catalyst and a method for producing an olefin polymer can be provided.

First, the olefin polymerization catalyst according to the present invention will be described.
The olefin polymerization catalyst according to the present invention is an olefin polymerization catalyst comprising a mixture of a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound, an organoaluminum compound, and inorganic oxide particles. There,
The inorganic oxide particles are characterized in that the number ratio of primary particles is 50 to 100%, and the average particle size is 1/100 or less of the average particle size of the solid catalyst component. .

In the olefin polymerization catalyst according to the present invention, examples of the magnesium atom supply source (raw material) constituting the solid catalyst component include various magnesium compounds.
Examples of the magnesium compound include one or more selected from dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium.
Among these magnesium compounds, dialkoxymagnesium is preferable, and specific examples include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, and the like. Magnesium is particularly preferred.
The dialkoxymagnesium may be obtained by reacting magnesium metal with an alcohol in the presence of a halogen or a halogen-containing metal compound.
The magnesium compounds may be used alone or in combination of two or more.

The dialkoxymagnesium is preferably in the form of granules or powder, and those having an indeterminate or spherical particle shape are suitable.
For example, when the magnesium compound is spherical dialkoxymagnesium, a polymer powder having a better particle shape (more spherical) and a narrow particle size distribution can be easily obtained, and the resulting polymer powder during the polymerization operation The handling operability of the pipe is improved, and blockage of piping caused by fine powder contained in the generated polymer powder can be easily suppressed.

The spherical dialkoxymagnesium does not necessarily need to be a true sphere, and includes an oval shape or a potato shape. Specifically, the shape of the particle is determined by the area S and the circumference L of the particle. Is suitably 3 or less, more suitably 1 or 2 and even more suitably 1 to 1.5.
In this application document, the circularity of dialkoxymagnesium refers to the area S of each particle obtained by photographing 500 or more dialkoxymagnesium particles with a scanning electron microscope and processing the photographed particles with image analysis processing software. And the perimeter L, and the circularity of each dialkoxymagnesium particle is represented by the following formula: Circularity of each dialkoxymagnesium particle = L ² ÷ (4π × S)
This means the arithmetic average value when calculated by (1). The closer the particle shape is to a perfect circle, the closer the circularity is to 1.

The magnesium compound preferably has an average particle size of 1 to 200 μm, more preferably 5 to 150 μm.
When the magnesium compound is spherical dialkoxymagnesium, the average particle size is preferably 1 to 100 μm, more preferably 5 to 50 μm, and even more preferably 10 to 40 μm.

In the present application documents, the average particle size of the magnesium compound is the average particle size D ₅₀ (particle size of 50% in the cumulative particle size distribution in the volume cumulative particle size distribution) when measured using a laser light scattering diffraction particle size analyzer. ).

The magnesium compound preferably has a narrow particle size distribution with a small particle size and a coarse particle size.
Specifically, particles having a particle size of 5 μm or less are preferably 20% or less, more preferably 10% or less.
On the other hand, particles having a particle size of 100 μm or more are preferably 10% or less, more preferably 5% or less.
Further, the particle size distribution is ln (D ₉₀ / D ₁₀ ) (where D ₉₀ is 90% of the cumulative particle size in the volume cumulative particle size distribution, and D ₁₀ is 10% of the cumulative particle size in the volume cumulative particle size distribution. In this case, it is preferably 3 or less, more preferably 2 or less.

  The spherical dialkoxymagnesium can be produced by, for example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-8- This is exemplified in Japanese Patent No. 73388.

  The magnesium compound is preferably in the form of a solution or a suspension at the time of the reaction, and the reaction can suitably proceed by being in the form of a solution or a suspension.

When the magnesium compound is a solid, the magnesium compound can be made into a solution-like magnesium compound by dissolving in a solvent capable of solubilizing the magnesium compound, or suspended in a solvent not having the solubilizing ability of the magnesium compound. By turbidity, a magnesium compound suspension can be obtained.
When the magnesium compound is in a liquid form, it may be used as it is as a solution-like magnesium compound, or it may be further dissolved in a solvent having a solubilizing ability of the magnesium compound and used as a solution-like magnesium compound. .

In the olefin polymerization catalyst according to the present invention, examples of the supply source (raw material) of titanium atoms and halogen atoms constituting the solid catalyst component include various titanium halogen compounds.
Although it does not restrict | limit especially as a titanium halogen compound, following general formula (IV)
Ti (OR ⁶ ) _s X _4-s (IV)
(Wherein R ⁶ represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, and s is an integer of 0 or 1 to 3). It is suitable that it is 1 or more types of the compounds selected from the titanium halide or the alkoxy titanium halide group.

Examples of the titanium halide include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.
Further, as the alkoxy titanium halide, methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium One or more types selected from dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride, and the like can be given.
As the titanium halogen compound, titanium tetrahalide is preferable, and titanium tetrachloride is more preferable.
These titanium halogen compounds can be used alone or in combination of two or more.

  In the olefin polymerization catalyst according to the present invention, the internal electron donating compound constituting the solid catalyst component includes phthalic acid diester, malonic acid diester, maleic acid diester, succinic acid diester, alkoxyalkyl ester, cyclohexene dicarboxylic acid diester and One or more selected from cyclohexanedicarboxylic acid diesters may be mentioned.

  The internal electron donating compound is preferably at least one selected from phthalic acid diester, malonic acid diester, alkyl-substituted malonic acid diester, maleic acid diester, succinic acid diester, cyclohexene dicarboxylic acid diester and cyclohexanedicarboxylic acid diester. One or more selected from diesters, malonic acid diesters, alkyl-substituted malonic acid diesters, succinic acid diesters, cyclohexene dicarboxylic acid diesters and cyclohexane dicarboxylic acid diesters are more preferred, selected from phthalic acid diesters, cyclohexene dicarboxylic acid diesters and cyclohexane dicarboxylic acid diesters More preferably, one or more phthalic acid diesters, 1-cyclohexene-1,2-dicarboxylic acid die Le, 4-cyclohexene-1,2-dicarboxylic acid diester, and cyclohexane are more preferable one or more kinds selected from dicarboxylic acid diesters, one or more selected from phthalate -n- butyl and diisobutyl phthalate is more preferable.

  In the olefin polymerization catalyst according to the present invention, the solid catalyst component can be prepared by, for example, contacting and reacting a magnesium compound, a titanium halogen compound, and an internal electron donating compound, and then washing.

  The contact between the magnesium compound, the titanium halogen compound, and the first internal electron donating compound is preferably carried out with stirring in an inert gas atmosphere in a state where moisture and the like are removed.

  The contact temperature of each component may be a relatively low temperature range around room temperature when it is simply brought into contact and mixed by stirring, or when it is modified by dispersing or suspending, but it may be reacted after contact. In the case of obtaining a product, the reaction rate and reaction control are facilitated, so that the temperature is preferably 40 to 130 ° C. Further, the stirring time is preferably 1 minute or longer, more preferably 10 minutes or longer, and further preferably 30 minutes or longer.

The washing treatment after the reaction is preferably performed using a hydrocarbon compound that is liquid at room temperature as a cleaning agent. Such hydrocarbon compound preferably does not contain a halogen atom and is liquid at room temperature. Liquid aromatic hydrocarbon compounds or saturated hydrocarbon compounds are preferred.
Specifically, linear or branched aliphatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. such as hexane, heptane, decane, and methylheptane, and alicyclic hydrocarbons having a boiling point of 50 to 150 ° C. such as cyclohexane and ethylcyclohexane. One or more types selected from compounds, aromatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. such as toluene, xylene, and ethylbenzene can be used.

In the olefin polymerization catalyst according to the present invention, the solid catalyst component preferably has a magnesium atom content of 10 to 70% by mass, more preferably 10 to 50% by mass, and 15 to 40% by mass. %, More preferably 15 to 25% by mass.
The solid catalyst component preferably has a titanium atom content of 0.5 to 8.0% by mass, more preferably 1.0 to 6.0% by mass, and 4.0 to 4%. More preferably, it is 5% by mass.
Further, the solid catalyst component preferably has a halogen atom content of 20 to 85% by mass, more preferably 30 to 80% by mass, still more preferably 40 to 75% by mass, 45 What is -70 mass% is still more preferable.
In addition, the solid catalyst component preferably has an internal electron donating compound content of 1.0 to 15.0% by mass, more preferably 3.0 to 13.0% by mass. What is 0.0-11.0 mass% is still more preferable.

In the olefin polymerization catalyst according to the present invention, the average particle size of the solid catalyst component is preferably 1 to 100 μm, more preferably 5 to 70 μm.
When the average particle diameter of the solid catalyst component is within the above range, the inorganic oxide particles are sufficiently dispersed on the surface of each solid catalyst component particle, and the inorganic oxide particles are dispersed at the interface of the solid catalyst component particle. Because it can be present, it suppresses the formation of aggregates in olefin polymerization catalysts, and effectively reduces particle aggregation and particle collapse due to local polymerization reactions that cause fine powder polymers during olefin polymerization. can do.

In the present application documents, the average particle diameter of the solid catalyst component is the average particle diameter D ₅₀ (50% in cumulative particle size distribution in the volume cumulative particle size distribution) as measured using a laser light scattering diffraction particle size analyzer. Diameter).

  The catalyst for olefin polymerization according to the present invention comprises a mixture of an organoaluminum compound, inorganic oxide particles, and an external electron donating compound used as necessary, together with a solid catalyst component.

As said organoaluminum compound, the following general formula (I);
R ¹ _p AlQ _3-p (I)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is a real number of 0 <p ≦ 3, and when a plurality of R ¹ are present, each R ¹ is And may be the same or different, and when a plurality of Q are present, each Q may be the same or different).

In the organoaluminum compound represented by the general formula (I), R ¹ is an alkyl group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. And isobutyl group.

  In the organoaluminum compound represented by the above general formula (I), Q represents a hydrogen atom or a halogen atom. When Q is a halogen atom, examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the organoaluminum compound represented by the general formula (I), when a plurality of R ¹ are present, each R ¹ may be the same or different. When a plurality of Q are present, each Q may be the same. May be different.

  Specific examples of the organoaluminum compound represented by the general formula (I) include one or more selected from triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride. Triisobutylaluminum is preferred.

The mixture constituting the olefin polymerization catalyst according to the present invention may be a mixture of the solid catalyst component, an organoaluminum compound, and an external electron donating compound.
In the olefin polymerization catalyst according to the present invention, examples of the external electron donating compound include organic compounds containing an oxygen atom or a nitrogen atom. Specific examples include alcohols, phenols, ethers and esters. , Ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds, especially organosilicon compounds having a Si—O—C bond.

  Among the external electron-donating compounds, esters such as ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate 1,3-diethers and organosilicon compounds containing Si—O—C bonds are preferred, and organosilicon compounds having Si—O—C bonds are particularly preferred.

Examples of the external electron donating compound include the following general formula (II):
R ² _q Si (OR ³ ) _4-q (II)
(In the formula, R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a vinyl group, an allyl group, an aralkyl group, an alkylamino group having 1 to 12 carbon atoms, or carbon. In the case where a dialkylamino group having 1 to 12 and a plurality of R ² are present, each R ² may be the same or different, and R ³ is an alkyl or cycloalkyl group having 1 to 4 carbon atoms. , A phenyl group, a vinyl group, an allyl group, or an aralkyl group, and when a plurality of R ³ are present, each R ³ may be the same or different, and q is an integer of 0 ≦ q ≦ 3. )
An organosilicon compound selected from the following general formula (III):
(R ⁴ R ⁵ N) _r SiR ⁶ _4-r (III)
(In the formula, R ⁴ and R ⁵ are each a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or a cyclohexane having 3 to 20 carbon atoms. An alkyl group or an aryl group, which may be the same or different, and R ⁴ and R ⁵ may be bonded to each other to form a ring, and R ⁶ is a straight chain having 1 to 20 carbon atoms or 3 carbon atoms; 20 branched alkyl group, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group or an aryl group having 3 to 20 carbon atoms, if R ⁶ is plural, R ⁶ may be the same or different R is an integer from 1 to 3)
One or more selected from aminosilane compounds represented by the formula:

In the compound represented by the general formula (II), when R ² is an alkyl group, the carbon number thereof is 1 to 12, preferably 1 to 6, and more preferably 1 to 4. .
In the compound represented by the general formula (II), when R ² is a cycloalkyl group, the carbon number thereof is 3 to 12, preferably 3 to 8, and more preferably 4 to 6. preferable.
In the compound represented by the general formula (II), when R ² is an alkylamino group, the carbon number thereof is 1 to 12, preferably 1 to 10, and more preferably 2 to 8. preferable.
In the compound represented by the general formula (II), when R ² is a dialkylamino group, the carbon number thereof is 1 to 12, preferably 1 to 10, and more preferably 2 to 8. preferable.

In the compound represented by the general formula (II), when R ³ is an alkyl group, the carbon number thereof is 1 to 4, preferably 1 to 3, and more preferably 1 to 2. .
In the compound represented by the general formula (II), when R ³ is a cycloalkyl group, the number of carbon atoms is preferably 3 to 6, more preferably 4 to 6, and still more preferably 5 to 6.

In the compound represented by the general formula (II), q is an integer of 0 ≦ q ≦ 3,
It is preferably 1 or 2.

  Examples of the organosilicon compound represented by the general formula (II) include phenylalkoxysilane, alkylalkoxysilane, phenyl (alkyl) alkoxysilane, vinylsilane, allylsilane, cycloalkylalkoxysilane, cycloalkyl (alkyl) alkoxysilane, (alkylamino) ) Alkoxysilane, alkyl (alkylamino) alkoxysilane, alkyl (dialkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, (polycyclic amino) alkoxysilane, (alkylamino) alkylsilane, (dialkylamino) alkylsilane , Cycloalkyl (alkylamino) alkylsilane, (polycyclic amino) alkylsilane, etc., among which di-n-propyldimethoxysilane, diisopropyl Dimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyl Dimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyl Dimethoxysilane, cyclohexylcyclopentyldiethoxysilane 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexyl (cyclopentyl) dimethoxysilane, bis (ethylamino) methylethylsilane, t-butylmethylbis (ethylamino) silane, bis ( Ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane, diethylaminotriethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane Bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, bis (methylamino) di-t-butylsilane Bis (ethylamino) dicyclopentyl silane and bis (ethylamino) one or more selected from diisopropyl silane are preferred.

In the compound represented by the general formula (III), when R ⁴ or R ⁵ is a linear alkyl group, the carbon number thereof is 1 to 20, preferably 1 to 12, and preferably 1 to 10 It is more preferable that
In the compound represented by the general formula (III), when R ⁴ or R ⁵ is a branched alkyl group, the carbon number thereof is 3 to 20, preferably 3 to 12, and preferably 3 to 10 It is more preferable that
In the compound represented by the general formula (III), when R ⁴ or R ⁵ is a cycloalkyl group, the carbon number thereof is 3 to 20, preferably 3 to 12, and preferably 3 to 10. It is more preferable.

In the compound represented by the general formula (IV), when R ⁶ is a linear alkyl group, the carbon number thereof is 1 to 20, preferably 1 to 12, and preferably 1 to 10. Is more preferable.
In the compound represented by the general formula (IV), when R ⁶ is a branched alkyl group, the carbon number thereof is 3 to 20, preferably 3 to 12, and preferably 1 to 10. More preferred.
In the compound represented by the general formula (IV), when R ⁶ is a cycloalkyl group, the carbon number thereof is 3 to 20, preferably 3 to 12, and more preferably 1 to 10. preferable.

  In the compound represented by the general formula (III), r is an integer of 1 to 3, and preferably 1 or 2.

  Examples of the aminosilane compound represented by the general formula (III) include alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, trialkyl (alkylamino) silane, and the like. Selected from (ethylamino) methylethylsilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane, etc. Among them, one or more selected from t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane and the like are preferable.

  In the catalyst for olefin polymerization according to the present invention, the external electron donating compound is at least one selected from the organosilicon compound represented by the general formula (II) and the aminosilane compound represented by the general formula (III). Is preferably used.

In the catalyst for olefin polymerization according to the present invention, the inorganic oxide particle means a dispersion of primary particles, which means solid oxide particles having an average particle size of 100 nm or less (nanosize). Examples of such inorganic oxide particles include oxides of elements that are contained in Group 1 to Group 16 elements on the periodic table and are solid at room temperature. Examples of such oxides include one or more selected from silica (silicon oxide), titanium oxide, magnesium oxide, zinc oxide, zirconium oxide, alumina (aluminum oxide), iron oxide, and the like.
The inorganic oxide particles are preferably the above-described oxide particles that are substantially spherical in shape.
As the inorganic oxide particles, nano silica is preferable. Here, nano silica means nano-sized silica, that is, silica nanoparticles. The method for producing nanosilica is not particularly limited, and dry fumed silica and wet colloidal silica can be applied. Examples of the nanosilica include, for example, JP2014-208585A and JP2015-117137A. What was manufactured by the method as described in 1 can be used conveniently.
In the olefin polymerization catalyst according to the present invention, the inorganic oxide particles preferably have an average particle size of more than 0 nm and 200 nm or less, more preferably 5 to 200 nm, and more preferably 5 to 100 nm. Is more preferable, and what is 10-100 nm is still more preferable.

The average particle diameter of the inorganic oxide particles is preferably 1/100 or less (0.01 or less) of the average particle diameter of the solid catalyst component, and 6/1000 or less (0.006 or less). Is more preferably 3/1000 or less (0.003 or less).
That is, the ratio represented by the average particle diameter of the inorganic oxide particles / the average particle diameter of the solid catalyst component is preferably 1/100 or less, more preferably 6/1000 or less, and 3/1000 or less. More preferably.
When the average particle diameter of the inorganic oxide particles is within the above range, the inorganic oxide particles can be easily highly dispersed in the polymerization catalyst when the polymerization catalyst is formed.

In the present application documents, the average particle diameter of the inorganic oxide particles and the average particle diameter of the solid catalyst component are the average particle diameter D ₅₀ (volume integration) when measured using a laser light scattering diffraction particle size analyzer. Mean particle size of 50% in cumulative particle size distribution).

  The shape of the inorganic oxide particles is not particularly limited, but spherical inorganic oxide particles are preferable.

In the present application document, the true density of the inorganic oxide particles is preferably 2.1 g / cm ³ or more, and more preferably 2.2 g / cm ³ or more. The upper limit of the true density of the inorganic oxide particles is not particularly limited, but is preferably 2.5 g / cm ³ .

  In the present application documents, the true density of the inorganic oxide particles is set in an environment maintained at a constant temperature using a true density measuring device after standing in an atmosphere of 40 ° C. and 80% relative humidity for 72 hours. It means a value measured by the gas phase substitution method for calculating the true density from the volume of helium gas occupying a certain volume. Examples of the true density measuring device by the gas phase substitution method include Ultrapycnometer 1000 manufactured by Cantachrome.

In this application, the specific surface area of the inorganic oxide particles is not particularly limited but is preferably 10 to 500 m ² / g, more preferably from 20 to 400 m ² / g, more preferably 30~300m ² / g.

In the present application document, as the inorganic oxide particles, those having a low content of primary particle aggregates (secondary particles) are preferable, and the number ratio of the primary particles contained in the powder of the inorganic oxide particles is 50% to 100%, preferably 60% to 100%, more preferably 70% to 100%, and even more preferably 75% to 100%.
In the present application document, the number ratio of the primary particles contained in the powder of inorganic oxide particles means that the powder of inorganic oxide particles is dispersed in an organic solvent such as alcohol or hydrocarbon compound and dried. Later, when 400 particles were randomly measured with a scanning electron microscope and the number of primary particles (non-aggregated) was X, (X / 400) × 100 Means a calculated value.
The number ratio of the particles composed of the primary particles is considered to correspond to the number ratio of the primary particles of the inorganic oxide particles in the olefin polymerization catalyst composed of the mixture of the solid catalyst component, the organoaluminum compound and the inorganic oxide particles. The oxide particles exist exclusively as primary particles in the olefin polymerization catalyst.
When the number ratio of the primary particles contained in the powder of inorganic oxide particles is within the above range, the amount of fine powder and coarse powder in the resulting olefin polymer when subjected to olefin polymerization The amount of generated olefins can be significantly reduced, and olefin polymers having a narrow particle size distribution can be produced effectively.

The catalyst for olefin polymerization according to the present invention includes a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound, an organoaluminum compound, inorganic oxide particles, and an external used as necessary. A mixture of an electron-donating compound and the presence of such inorganic oxide particles improves the dispersibility of the olefin polymerization catalyst and prevents local heat generation in the polymerization vessel. It is considered that the particle breakage is less likely to occur, and the generation amount of the fine powder polymer as well as the coarse powder polymer can be suppressed.
It is also considered that the amount of fine powder generated can be suppressed by selectively poisoning the active sites of the fine powder particles present in the solid catalyst component with a trace amount of hydroxyl groups present on the inorganic oxide particles.

In the present application document, the inorganic oxide particles may be subjected to a surface treatment with a silane coupling agent or the like.
The silane coupling agent includes a structure containing one or more groups selected from phenyl group, vinyl group, epoxy group, methacryl group, amino group, ureido group, mercapto group, isocyanate group and acrylic group, together with three alkoxy groups. And those having a structure containing two cycloalkyl groups together with two alkoxy groups, and those having a structure containing a phenyl group or a vinyl group together with three alkoxy groups are preferred.
Surface treatment was performed by adding organosilazane having a structure in which two hydrogen atoms constituting ammonia were each substituted with a trialkylsilyl group in a molar ratio of 2 to 10 times that of the silane coupling agent. May be.
By the surface treatment, the hydroxyl group present on the surface of the inorganic oxide particles is substituted with a functional group derived from the silane coupling agent, and the hydroxyl group that deactivates the catalyst can be reduced.
In addition, in this invention, the said inorganic oxide particle may be used individually by 1 type, or may be used in combination of 2 or more type.

The olefin polymerization catalyst according to the present invention preferably has an inorganic oxide particle content of 2 parts by mass or more with respect to 100 parts by mass of the solid catalyst component, and the inorganic oxide particles with respect to 100 parts by mass of the solid catalyst component. The content is more preferably 5 parts by mass or more, the content of the inorganic oxide particles with respect to 100 parts by mass of the solid catalyst component is more preferably 10 parts by mass or more, and the inorganic content with respect to 100 parts by mass of the solid catalyst component. It is more preferable that the content of the oxide particles is 50 parts by mass or more.
The upper limit of the content of the inorganic oxide particles is not particularly limited, but in the olefin polymerization catalyst according to the present invention, the content of the inorganic oxide particles is 100 parts by mass or less with respect to 100 parts by mass of the solid catalyst component. Is preferred.
When the content of the inorganic oxide particles with respect to 100 parts by mass of the solid catalyst component is within the above range, the surface of the solid catalyst component can be sufficiently covered with the inorganic oxide particles, and the dispersibility of the olefin polymerization catalyst. Can be effectively improved, local heat generation in the polymerization vessel can be suppressed, and destruction of the polymerization catalyst particles can be suitably suppressed.

In the olefin polymerization catalyst according to the present invention, the content ratios of the solid catalyst component, the organoaluminum compound and the external electron donating compound can be arbitrarily selected within the range where the effects of the present invention can be obtained, and are not particularly limited.
The catalyst for olefin polymerization according to the present invention preferably contains 1 to 2000 moles, more preferably 50 to 1000 moles of organoaluminum compound per mole of titanium atoms in the solid catalyst component.
The olefin polymerization catalyst according to the present invention contains 1 to 200 mol of external electron donating compounds in total per mol of titanium atom in the solid catalyst component contained in the olefin polymerization catalyst. Is more preferable, 2 to 150 mol is more preferable, and 5 to 100 mol is more preferable.
Furthermore, the olefin polymerization catalyst according to the present invention preferably contains 0.001 to 10 mol of an external electron donating compound in total per mol of the organoaluminum compound contained in the olefin polymerization catalyst. 0.002 to 2 mol is more preferable, and 0.002 to 0.5 mol is more preferable.

  The olefin polymerization catalyst according to the present invention can be suitably produced by the method for producing an olefin polymerization catalyst according to the present invention.

  According to the present invention, there is provided an olefin polymerization catalyst capable of effectively producing an olefin polymer having a narrow particle size distribution by significantly reducing the amount of fine powder and coarse powder generated in the resulting olefin polymer. can do.

Next, a method for producing the olefin polymerization catalyst according to the present invention will be described.
In the method for producing a catalyst for olefin polymerization according to the present invention, the number ratio of particles composed of a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound, an organoaluminum compound and primary particles is 50 to 50. It is characterized by mixing inorganic oxide particles which are 100% and whose average particle size is 1/100 or less of the average particle size of the solid catalyst component.

In the method for producing an olefin polymerization catalyst according to the present invention, the details of the solid catalyst component, the organoaluminum compound, and the inorganic oxide particles are as described above, and external electron donating properties arbitrarily mixed with the above components. The details of the compound are also as described above.
In addition, the mixing amount of the inorganic oxide particles when mixing each of the above components also corresponds to the above content, and the mixing amount of the components other than the inorganic oxide particles is also in each component in the resulting catalyst. What is necessary is just to select suitably so that it may become content mentioned above.

  In the method for producing an olefin polymerization catalyst according to the present invention, the contact temperature when mixing each of the above components is not particularly limited, but is preferably lower than the boiling point of the organoaluminum compound, specifically, room temperature or lower. The temperature is preferably 0 to 20 ° C.

  In the method for producing an olefin polymerization catalyst according to the present invention, the mixing time (reaction time) when mixing the above components is not particularly limited, but is preferably 1 to 60 minutes, more preferably 2 to 40 minutes, 5-30 minutes is more preferable.

In the method for producing an olefin polymerization catalyst according to the present invention, the (a) solid catalyst component, (b) an organoaluminum compound, (c) an external electron donating compound, and (d) an inorganic oxide particle are mixed. The contact order is not particularly limited, and examples thereof include any of the following contact orders (i) to (v) (in the contact order of any of the following (i) to (v), (c) external electron donation (C) When the external compound is not used, the step of adding the external electron donating compound is omitted).
(I) (b) Organoaluminum compound → (c) External electron donating compound → (d) Inorganic oxide particles → (a) Solid catalyst component.
(Ii) (b) Organoaluminum compound → (d) Inorganic oxide particles → (c) External electron donating compound → (a) Solid catalyst component.
(Iii) (d) inorganic oxide particles → (b) organoaluminum compound → (c) external electron donating compound → (a) solid catalyst component.
(Iv) (d) inorganic oxide particles → (c) external electron donating compound → (a) solid catalyst component → (b) organoaluminum compound.
(V) (b) Organoaluminum compound → (c) External electron donating compound → ((a) solid catalyst component + (d) inorganic oxide particles).
In the above (i) to (v), the arrow (→) indicates the contact order. For example, (b) organoaluminum compound → (c) external electron donating compound → (d) inorganic oxide particle → (a The solid catalyst component is obtained by mixing (b) an organoaluminum compound and (c) an external electron donating compound and bringing them into contact with each other, and then (d) inorganic oxide particles and (a) a solid catalyst on the obtained contact product. It means that the components are mixed and contacted in sequence.
In addition, (b) organoaluminum compound → (c) external electron donating compound → ((a) solid catalyst component + (d) inorganic oxide particles) comprises (b) organoaluminum compound and (c) external electron donation. This means that (a) the solid catalyst component and (d) inorganic oxide particles are simultaneously mixed and brought into contact with the obtained contact product after mixing and contacting with the active compound.

Among the contact orders, any one of the contact orders (i) to (iii) is preferable, and the contact order (i) or (ii) is more preferable.
By mixing (a) the solid catalyst component, (b) the organoaluminum compound, (c) the external electron donating compound and (d) the inorganic oxide particles in the above order, the inorganic oxide particles are subjected to olefin polymerization. The catalyst for olefin polymerization highly dispersed in the catalyst for use can be easily obtained.

In the present application documents, the above (a) solid catalyst component, (b) organoaluminum compound, (d) inorganic oxide particles and optionally used (c) external electron donating compound (hereinafter, Mixing each component) means an operation of mixing each component in a dry state or dispersing or suspending each component in an appropriate amount of liquid (solvent) and homogenizing it, and destroying each component. The method is not particularly limited as long as it can be homogenized without any limitation, and includes a method accompanied by a stirring process as appropriate.
Further, in the present application documents, (a) the solid catalyst component, (b) the organoaluminum compound, (d) the inorganic oxide particles and the necessary component (c) the external electron donating compound (hereinafter referred to as each component). A mixture means the thing obtained by giving the said mixing process.
The above components may be mixed manually or using a mixer.
As the mixer, one or more selected from a container rotation type mixing device such as a V-type mixer, a stirring type mixing device such as a tank or a reactor equipped with a stirrer, a mixing and grinding device such as a vibration mill and a ball mill, and the like. Can be mentioned. Among the above-described mixing and pulverizing apparatuses, a container rotating type mixing apparatus is preferable in that it can suppress particle breakage of the solid catalyst component.
The mixing method is particularly preferably a method in which each component is added to a solvent to form a slurry and then mixed with a spray dryer.

  According to the present invention, there is provided a method for producing an olefin polymerization catalyst capable of significantly producing an olefin polymer having a narrow particle size distribution by significantly reducing the amount of fine powder and coarse powder produced in the olefin polymer. Can be provided.

Next, the manufacturing method of the olefin polymer which concerns on this invention is demonstrated.
The method for producing an olefin polymer according to the present invention is characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst according to the present invention.
In the method for producing an olefin polymer according to the present invention, the details of the catalyst for olefin polymerization and the method for producing the same according to the present invention are as described above.

  Examples of the olefins used for polymerization include one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like. One or more selected from butenes are preferred, and propylene is more preferred.

  Polymerization of olefins can be carried out in the presence or absence of an organic solvent, and olefin monomers such as propylene can be used in either a gas or liquid state.

  As a method for polymerizing olefins, a conventionally known method used for polymerizing 1-olefins having 2 to 10 carbon atoms can be used. For example, a gas or liquid monomer is supplied in the presence of an organic solvent to perform polymerization. Examples include slurry polymerization, bulk polymerization in which polymerization is performed in the presence of a liquid monomer such as liquefied propylene, and gas phase polymerization in which polymerization is performed in the presence of a gaseous monomer. The polymerization reaction is performed by any of these methods. Polymerization by gas phase polymerization is preferred.

  In addition, for example, the method described in Japanese Patent No. 2578408, the continuous gas phase polymerization method described in Japanese Patent No. 4392064, Japanese Patent Application Laid-Open No. 2009-292964, and the polymerization method described in Japanese Patent No. 2766523 are also applied. Is possible. In addition, each said polymerization method can be performed by either a batch type or a continuous type. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  In the case of polymerizing olefins using the olefin polymerization catalyst according to the present invention, examples of the polymerization reactor may include a reactor such as an autoclave with a stirrer and a fluidized tank. The powdered polymer can be contained in a stationary phase and moved using a stirrer or a fluidized bed.

The molecular weight of the polymer to be obtained can be adjusted and set over a wide range by adding a regulator commonly used in the polymerization technique, for example, hydrogen.
In order to remove the heat of polymerization, a liquid easily volatile hydrocarbon such as butane may be supplied and vaporized in the polymerization zone.

The polymerization temperature is preferably 200 ° C. or lower, more preferably 100 ° C. or lower, and further preferably 50 to 90 ° C.
The polymerization pressure is preferably normal pressure to 10 MPa, more preferably normal pressure to 5 MPa, and even more preferably 1 to 4 MPa.

  In the method for producing an olefin polymer according to the present invention, the amount of fine powder having a particle size of 75 μm or less is preferably 0 to 1% by mass, and 0 to 0.7% by mass. More preferably, it is more preferably 0 to 0.5% by mass.

  In the method for producing an olefin polymer according to the present invention, the amount of coarse powder having a particle size of 2800 μm or more is preferably 0 to 5 mass%, and preferably 0 to 3 mass%. It is more preferable, and it is still more preferable that it is 0-1 mass%.

In the method for producing an olefin polymer according to the present invention, the obtained olefin polymer preferably has a particle size distribution index calculated by the following formula of 0 to 1.1, 0.1 to 0.8. It is more preferable that it is 0.3 to 0.5.
The particle size distribution index _{(SPAN) = (D 90 -D} 10) / D 50
(However, D ₉₀ means a volume cumulative particle size of 90% particle size, D ₅₀ means a volume cumulative particle size of 50% particle size, and D ₁₀ means a volume cumulative particle size of 10% particle size.)

  In the present application documents, the fine and coarse powders of the olefin polymers and the particle size distribution index (SPAN) are measured using a digital image analysis type particle size distribution measuring device (Camsizer, Horiba, Ltd.). Value.

  According to the present invention, the amount of fine powder and coarse powder generated is remarkably reduced, and an olefin polymer having a narrow particle size distribution can be easily produced.

(Example)
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

(Production Example 1)
<Preparation of Solid Catalyst Component (C-1) for Olefin Polymerization>
A 200 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 10 g of spherical diethoxymagnesium having an average particle size of 43.1 μm, 50 ml of toluene and 3.6 ml of di-n-butyl phthalate. Suspended. Next, the obtained suspension solution was placed in a mixed solution of 26 ml of toluene and 24 ml of titanium tetrachloride previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas inside. The whole amount was added over 1 hour. After completion of the addition, the temperature in the reaction system was increased to 90 ° C. while stirring, and the reaction temperature was maintained at 90 ° C. for 2 hours to cause a contact reaction.
After completion of the reaction, the obtained reaction product was washed 4 times with 100 ml of toluene at 90 ° C., then 24 ml of titanium tetrachloride and 76 ml of toluene were added, the temperature was raised, and contact reaction was carried out with stirring at 115 ° C. for 1 hour. .
The produced solid component was washed 10 times with 100 ml of n-heptane at 40 ° C. and then dried until the residual ratio of heptane became 20% by weight or less to obtain a powdered solid catalyst component (C-1).
When the obtained solid catalyst component was analyzed, the titanium content was 3.1% by mass, the average particle size (D ₅₀ ) was 38.9 μm, and the particle size distribution index (SPAN) was 0.8.

(Production Example 2)
<Preparation of Solid Catalyst Component (C-2) for Olefin Polymerization>
A 200 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 10 g of spherical diethoxymagnesium, 50 ml of toluene, and 5.1 ml of dimethyl diisobutylmalonate, and suspended. Next, the obtained suspension solution was placed in a mixed solution of 26 ml of toluene and 24 ml of titanium tetrachloride previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas inside. The whole amount was added over 1 hour. After completion of the addition, the temperature in the reaction system was increased to 115 ° C. while stirring, and the reaction temperature was maintained at 115 ° C. for 4 hours to cause a contact reaction.
After the completion of the reaction, the obtained reaction product was washed 4 times with 100 ml of toluene at 90 ° C., then added with 20 ml of titanium tetrachloride and 60 ml of toluene, heated up, and contacted with stirring at 100 ° C. for 2 hours. .
The produced solid component was washed 10 times with 100 ml of n-heptane at 40 ° C. and then dried until the residual ratio of heptane became 20% by weight or less to obtain a powdered solid catalyst component (C-2).
When the obtained solid catalyst component was analyzed, the titanium content was 2.2% by mass, the average particle size (D ₅₀ ) was 45.5 μm, and the particle size distribution index (SPAN) was 0.8.

(Production Example 3)
<Preparation of Solid Catalyst Component (C-3) for Olefin Polymerization>
Anhydrous magnesium chloride (75 g), decane (375 ml) and 2-ethylhexyl alcohol (300 g) were heated at 135 ° C. for 4 hours to form a homogeneous solution, and 2-ethoxyethyl-1-methyl carbonate (16.7 ml) was added to the solution. The obtained homogeneous solution was cooled to room temperature, and 113 ml of this homogeneous solution was charged dropwise into 300 ml of titanium tetrachloride maintained at -20 ° C over 45 minutes. After the dropwise addition, the liquid temperature was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 1.6 ml of 2-isopropyl 2-isopentyl-1,3-dimethoxypropane and 2-ethoxyethyl-1-methyl carbonate 0 .9 ml was added. Further, after stirring for 2 hours at the above temperature, the mixture was filtered and the solid part was washed with decane, and then dried with decane until the residual rate was 20% by weight or less, and the powdered solid catalyst component (C-3) Got.
When the obtained solid catalyst component was analyzed, the titanium content was 1.8% by mass, the average particle size (D ₅₀ ) was 9.0 μm, and the particle size distribution index (SPAN) was 1.0.

(Production Example 4)
<Preparation of solid catalyst component (C-4) for olefin polymerization>
A 500 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas was charged with 5.0 g of titanium trichloride, 9.0 g of anhydrous magnesium chloride, and 220 mL of tetrahydrofuran, and then stirred at 65 ° C. The temperature rose. After maintaining at 65 ° C. for 2 hours, 12.2 g of sorbitan monooleate (manufactured by Croda Japan Co., Ltd., Span 80) was added, and the reaction temperature at 65 ° C. was further maintained for 3 hours, and then the temperature was reduced to room temperature. .
Next, 13.5 g of nanosilica (manufactured by Admatechs, YC100C-SV2) was charged into a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and then the above solution lowered to room temperature was added. Stir for 2 hours. After stirring, the mixture was spray-dried with a spray dryer (spraying conditions: inlet temperature 150 ° C., outlet temperature 90 ° C.) to obtain a powdered solid catalyst component (C-4). The nanosilica used had a particle number ratio of 75% or more consisting of primary particles (not agglomerated) when 400 particles randomly extracted with a scanning electron microscope were measured.
When the obtained solid catalyst component was analyzed, the titanium content was 2.6% by mass, the average particle size (D ₅₀ ) was 10.1 μm, and the particle size distribution index (SPAN) was 1.5.
Here, the nano silica content in the formed solid catalyst component was 90 parts by mass with respect to 100 parts by mass of the solid catalyst component.

Example 1
<Formation of Olefin Polymerization Catalyst>
In an autoclave with a stirrer with an internal volume of 2200 ml replaced with nitrogen gas, 5 ml of n-heptane, 1.3 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane, an average particle diameter of 10 nm and a true density of 2.2 g Nanosilica (Admatex, YA010C-SV5) 0.4 mg / cm ³ was charged.
Next, the solid catalyst component (C-1) was charged in an amount equivalent to 0.0026 mmol in terms of titanium atom to form an olefin polymerization catalyst.
Here, the nanosilica used was 10 parts by mass with respect to 100 parts by mass of the solid catalyst component, and consisted of primary particles (aggregated) when 400 particles randomly extracted with a scanning electron microscope were measured. No) The number ratio of the particles was 60% or more.
The preparation conditions are shown in Table 1.

<Evaluation of propylene polymerization and obtained polymer>
The autoclave containing the catalyst for olefin polymerization formed as described above was charged with 2000 ml of hydrogen gas and 1400 ml of liquefied propylene, preliminarily polymerized at 20 ° C. for 5 minutes, and then heated to 70 ° C. for 1 hour of main polymerization. Went.
At this time, the propylene polymerization activity (PP activity) per 1 g of the solid catalyst component was calculated by the following formula.
(Propylene polymerization activity per 1 g of solid catalyst component (PP activity))
Polymerization activity (g-pp / g-catalyst) = mass of polymer obtained (g) / mass of solid catalyst component (g)
Moreover, about the obtained polymer, the bulk density (BD) of the polymer, the amount of fine powder in a polymer, the amount of coarse powder, and the particle size distribution index (SPAN) were measured.
The results are shown in Table 2.

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

<Measurement method of fine powder amount, coarse powder amount and polymer particle size distribution index (SPAN) in polymer>
The amount of fine powder, coarse powder, and particle size distribution index (SPAN) in the polymer are measured using the digital image analysis type particle size distribution measuring device (Horiba Seisakusho Co., Ltd.) under the following measurement conditions. The distribution was automatically measured, and the content (mass%) of each was measured with the amount of particles having a particle size of 75 μm or less as the amount of fine powder and the amount of particles having a particle size of 2800 μ or more as the amount of coarse powder.
The volume-based cumulative particle size obtained by the above measurement method is 90% particle size (D ₉₀ ), the volume-based cumulative particle size is 50% particle size (D ₅₀ ), and the volume-based cumulative particle size is 10% particle size ( From the value of D ₁₀ ), the particle size distribution index (SPAN) was calculated by the following method.
The particle size distribution index _{(SPAN) = (D 90 -D} 10) / D 50
The results are shown in Table 2.
(Measurement conditions of digital image analysis type particle size distribution measuring device)
Funnel position: 6mm
Camera cover area: Basic camera less than 3%, Zoom camera less than 10% Target cover 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 per particle SPHT (sphericity) fitting: 1
Upper limit of class: 50 points are selected in the logarithmic scale range of 32 μm to 4000 μm

(Example 2)
<Preparation of Olefin Polymerization Catalyst>
In an autoclave equipped with a stirrer with an internal volume of 2200 ml replaced with nitrogen gas, 1.3 mmol of triethylaluminum and 0.13 mmol of cyclohexylmethyldimethoxysilane were added. Thereafter, the solid catalyst component (C-1) obtained in Production Example 1 in an amount equivalent to 0.0026 mmol in terms of titanium atom, and nanosilica having an average particle diameter of 100 nm and a true density of 2.2 g / cm ³ (manufactured by Admatechs) , YC100C-SV2) 0.4 mg of a mixture was charged to form an olefin polymerization catalyst.
Here, the nanosilica used was 10 parts by mass with respect to 100 parts by mass of the solid catalyst component, and consisted of primary particles (aggregated) when 400 particles randomly extracted with a scanning electron microscope were measured. No) The number ratio of the particles was 75%.
The preparation conditions are shown in Table 1.
Propylene polymerization and evaluation of the obtained polymer were carried out in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 1)
Except that no nanosilica was added during the preparation of the olefin polymerization catalyst, the formation of an olefin polymerization catalyst, propylene polymerization, and evaluation of the resulting polymer were performed in the same manner as in Example 1.
The results are shown in Table 2.

(Example 3)
<Preparation of Olefin Polymerization Catalyst>
Instead of the solid catalyst component (C-1) obtained in Production Example 1, the same amount of the solid catalyst component (C-2) obtained in Production Example 2 was used, and the amount of nanosilica added was changed from 0.4 mg to 2. An olefin polymerization catalyst was formed in the same manner as in Example 1 except that the amount was changed to 8 mg.
Here, the used nano silica was 50 parts by mass with respect to 100 parts by mass of the solid catalyst component. The preparation conditions are shown in Table 1.
Propylene polymerization and evaluation of the obtained polymer were carried out in the same manner as in Example 1. The results are shown in Table 2.

(Example 4)
Instead of the solid catalyst component (C-1) obtained in Production Example 1, the same molar amount of the solid catalyst component (C-2) obtained in Production Example 2 was used, and the amount of nanosilica added was 0.4 mg to 5. An olefin polymerization catalyst was formed in the same manner as in Example 1 except that the amount was changed to 7 mg.
Here, the used nano silica was 100 parts by mass (equivalent) with respect to 100 parts by mass of the solid catalyst component. The preparation conditions are shown in Table 1.
Propylene polymerization and evaluation of the resulting polymer were carried out in the same manner as in Example 1. The results are shown in Table 2.

(Example 5)
Instead of the solid catalyst component (C-1) obtained in Production Example 1, the solid catalyst component (C-2) obtained in the same mole of Production Example 2 was used, and the average particle size was 10 nm and the true density was Instead of 0.4 mg of nanosilica having 2.2 g / cm ³ (manufactured by Admatechs, YC100C-SV5), nanosilica having an average particle diameter of 100 nm and a true density of 2.2 g / cm ³ (manufactured by Admatechs, YA100C-SV2) An olefin polymerization catalyst was formed in the same manner as in Example 1 except that 0.6 mg was used.
Here, the used nano silica was 10 parts by mass with respect to 100 parts by mass of the solid catalyst component. The preparation conditions are shown in Table 1.
Propylene polymerization and evaluation of the resulting polymer were carried out in the same manner as in Example 1. The results are shown in Table 2.

(Example 6)
Instead of the solid catalyst component (C-1) obtained in Production Example 1, the same molar solid catalyst component (C-2) obtained in Production Example 2 was used, and the average particle size was 10 nm and the true density was 2 .2g / cm ³ and a nanosilica (Admatechs Co., YC100C-SV5) true density 100nm average particle size in place of 0.4mg is 2.2 g / cm ³ nanosilica (Admatechs Co., YA100C- SV2) An olefin polymerization catalyst was formed in the same manner as in Example 1 except that 0.1 mg was used.
Here, the used nano silica was 2 parts by mass with respect to 100 parts by mass of the solid catalyst component. The preparation conditions are shown in Table 1.
Propylene polymerization and evaluation of the resulting polymer were carried out in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 2)
Instead of the solid catalyst component (C-1) obtained in Production Example 1, the same amount of the solid catalyst component (C-2) obtained in Production Example 2 was used. Further, nanosilica was added during the preparation of the olefin polymerization catalyst. Except not having added, it carried out similarly to Example 1, and formed the olefin polymerization catalyst, propylene polymerization, and evaluation of the obtained polymer. The results are shown in Table 2.

(Comparative Example 3)
Instead of the solid catalyst component (C-1) obtained in Production Example 1, the same molar solid catalyst component (C-2) obtained in Production Example 2 was used, and the average particle size was 10 nm and the true density was 2 .2g / cm ³ and a nanosilica (Admatechs Co., YC100C-SV5) true density 100nm average particle size in place of 0.4mg is 2.2 g / cm ³ nanosilica (Nippon Aerosil Co., Ltd., average particle An olefin polymerization catalyst was formed in the same manner as in Example 1 except that 0.1 mg of primary particles having a diameter of 10 nm aggregated into secondary particles having a particle diameter of 100 nm was used.
Here, the nanosilica used was 2 parts by mass with respect to 100 parts by mass of the solid catalyst component, and consisted of primary particles (aggregated) when 400 particles randomly extracted with a scanning electron microscope were measured. No) The number ratio of the particles was less than 30%.
Propylene polymerization and evaluation of the resulting polymer were carried out in the same manner as in Example 1. The results are shown in Table 2.

(Example 7)
<Preparation of Olefin Polymerization Catalyst>
Instead of the solid catalyst component (C-1), the same mole of the solid catalyst component (C-3) is used, and nanosilica having an average particle diameter of 10 nm and a true density of 2.2 g / cm ³ (Admatex Co., Ltd.) Manufactured by YC100C-SV5) 0.4 mg instead of 0.3 mg of nanosilica having an average particle size of 50 nm and a true density of 2.2 g / cm ³ (manufactured by Admatechs, YA100C-SV6) In the same manner as in Example 1, an olefin polymerization catalyst was formed.
Here, the used nanosilica is 5 parts by mass with respect to 100 parts by mass of the solid catalyst component, and is composed of primary particles (aggregates) when 400 particles randomly extracted by a scanning electron microscope are measured. The particle number ratio was 75% or more.
The preparation conditions are shown in Table 1.
Propylene polymerization and evaluation were carried out in the same manner as in Example 1. The results are shown in Table 2.

(Example 8)
<Preparation of Olefin Polymerization Catalyst>
A catalyst for olefin polymerization was prepared in the same manner as in Example 7, and propylene polymerization and evaluation were performed in the same manner as in Example 1 except that no external electron-donating compound was used during propylene polymerization. The results are shown in Table 2.

(Comparative Example 4)
Instead of 0.3 mg of nanosilica having a mean particle diameter of 50 nm and a true density of 2.2 g / cm ³ (manufactured by Admatechs, YA100C-SV6), the mean particle diameter is 100 nm and the true density is 2.2 g / cm ³ An olefin polymerization catalyst was formed in the same manner as in Example 7 except that 0.3 mg of certain nanosilica (manufactured by Admatechs, YC100C-SV2) was used.
Here, the used nano silica was 2 parts by mass with respect to 100 parts by mass of the solid catalyst component. The preparation conditions are shown in Table 1.
Propylene polymerization and evaluation of the resulting polymer were carried out in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 5)
Example 1 except that the solid catalyst component (C-3) in the same mole was used instead of the solid catalyst component (C-1), and nanosilica was not added during the preparation of the olefin polymerization catalyst. Similarly, formation of an olefin polymerization catalyst, propylene polymerization, and evaluation of the obtained polymer were performed. The results are shown in Table 2.

(Comparative Example 6)
<Preparation of Olefin Polymerization Catalyst>
Example 1 except that the same molar solid catalyst component (C-4) was used in place of the solid catalyst component (C-1), and that no nanosilica was added during the preparation of the olefin polymerization catalyst. Similarly, formation of an olefin polymerization catalyst, propylene polymerization, and evaluation of physical properties of the obtained polymer were performed. The results are shown in Table 2.

The catalysts for olefin polymerization obtained in Examples 1 to 8 were prepared from a mixture of a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound, an organoaluminum compound, and inorganic oxide particles. A catalyst for olefin polymerization, wherein the inorganic oxide particles have a primary particle number ratio of 50 to 100% and an average particle size of 1/100 or less of the average particle size of the solid catalyst component. The presence of a certain amount of inorganic oxide particles improves the dispersibility of the catalyst for olefin polymerization and prevents local heat generation in the polymerization vessel, so that the polymerization catalyst particles are less likely to be destroyed. In addition to suppressing the generation of fine powder polymer as well as coarse powder polymer, the minute amount of hydroxyl groups present on the inorganic oxide particles is present in the solid catalyst component. Also by selectively poisoning the active sites of the particles is believed to be capable of suppressing the fines emissions.
For this reason, from Table 2, in Examples 1 to 8, the amount of fine powder generated is significantly reduced, and the ratio of coarse powder particles in the olefin polymer is also reduced to obtain an olefin polymer having a narrow particle size distribution. It can be seen that the fluidity of the powder of the polymer is improved, and it is possible to effectively suppress process failures such as piping blockage during the production or transfer of the polymer and a decrease in the molding processability of the polymer.

  On the other hand, the catalysts for olefin polymerization obtained in Comparative Examples 1 to 6 were formed in the absence of inorganic oxide particles (Comparative Example 1, Comparative Example 2, Comparative Example 5, Comparative Example). Example 6), an aggregate of fine primary particles used as inorganic oxide particles (Comparative Example 3), and the average particle size of the inorganic oxide particles is 1 of the average particle size of the solid catalyst component. / Comparative Example 4 indicates that in Comparative Example 1 to Comparative Example 6 it is not possible to reduce the pulverization of the solid catalyst component itself and the particle breakage during the polymerization. It can be seen that the amount of fine powder generated cannot be suppressed, and it is not possible to suppress process failures such as piping blockage accompanying the generation of fine powder and deterioration of the molding processability of the polymer.

  According to the present invention, there is provided an olefin polymerization catalyst capable of effectively producing an olefin polymer having a narrow particle size distribution by significantly reducing the amount of fine powder and coarse powder generated in the resulting olefin polymer. In addition, a method for producing an olefin polymerization catalyst and a method for producing an olefin polymer can be provided.

Claims (7)

A catalyst for olefin polymerization comprising a solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound, an organic aluminum compound and a mixture of inorganic oxide particles,
Olefin polymerization, wherein the inorganic oxide particles have a primary particle number ratio of 50 to 100% and an average particle size of 1/100 or less of the average particle size of the solid catalyst component. Catalyst. 2. The olefin polymerization catalyst according to claim 1, wherein the inorganic oxide particles have an average particle diameter of 200 nm or less and a true density of 2.1 g / cm ³ or more.   The catalyst for olefin polymerization according to claim 1 or 2, wherein the content of the inorganic oxide particles with respect to 100 parts by mass of the solid catalyst component is 2 parts by mass or more. The organoaluminum compound is represented by the following general formula (I):
R ¹ _p AlQ _3-p (I)
(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is a real number of 0 <p ≦ 3, each of R ¹ if R ¹ there are a plurality of May be the same or different, and when there are multiple Qs, each Q may be the same or different)
The olefin polymerization catalyst according to any one of claims 1 to 3, which is represented by the following formula. The following general formula (II);
R ² _q Si (OR ³ ) _4-q (II)
(In the formula, R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, a vinyl group, an allyl group, an aralkyl group, an alkylamino group having 1 to 12 carbon atoms, or carbon. In the case where a dialkylamino group having 1 to 12 and a plurality of R ² are present, each R ² may be the same or different, and R ³ is an alkyl or cycloalkyl group having 1 to 4 carbon atoms. , A phenyl group, a vinyl group, an allyl group, or an aralkyl group, and when a plurality of R ³ are present, each R ³ may be the same or different, and q is an integer of 0 ≦ q ≦ 3. )
An organosilicon compound selected from the following general formula (III):
(R ⁴ R ⁵ N) _r SiR ⁶ _4-r (III)
(In the formula, R ⁴ and R ⁵ are each a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or a cyclohexane having 3 to 20 carbon atoms. An alkyl group or an aryl group, which may be the same or different, and R ⁴ and R ⁵ may be bonded to each other to form a ring, and R ⁶ is a straight chain having 1 to 20 carbon atoms or 3 carbon atoms; 20 branched alkyl group, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group or an aryl group having 3 to 20 carbon atoms, if R ⁶ is plural, R ⁶ may be the same or different R is an integer from 1 to 3)
The olefin polymerization catalyst according to any one of claims 1 to 4, comprising any one or more external electron donating compounds selected from the group consisting of aminosilane compounds represented by formula (1). The solid catalyst component containing a magnesium atom, a titanium atom, a halogen atom and an internal electron donating compound, the number ratio of particles composed of an organoaluminum compound and primary particles is 50 to 100%, and the average particle size of the solid catalyst component is A method for producing an olefin polymerization catalyst, comprising mixing inorganic oxide particles having an average particle diameter of 1/100 or less.   A method for producing an olefin polymer, comprising polymerizing olefins in the presence of the olefin polymerization catalyst according to any one of claims 1 to 5.