Solid catalyst component for olefin polymerization, method for producing solid catalyst component for olefin polymerization, catalyst for olefin polymerization, method for producing olefin polymer particles, and olefin polymer particles

Abstract

Provided is a solid catalytic component for olefin polymerization capable of suitably producing at high activity polymer particles having a suppressed content ratio of fine powder and reduced surface stickiness when used in the polymerization of an olefin.　The present invention is a solid catalytic component for olefin polymerization that includes magnesium, titanium, a halogen, and an internal electron-donating compound, the cross-sectional pore area rate being 10-50% and the ratio MXi / MXs of the cross-sectional pore area rate of a region of less than 50% of the radial direction (MXi) to the cross-sectional pore area rate of a region of 50% or more of the radial direction from the particle center (MXs) being 0.50-2.00.

Description

[Technical Field]

[0001] The present invention relates to a solid catalyst component for olefin polymerization, a method for producing a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for producing olefin polymer particles, and olefin polymer particles. [Background technology]

[0002] Conventionally, methods for polymerizing olefins, such as propylene homopolymerization and ethylene-propylene copolymerization, have been known, using a solid catalyst component for polymerizing olefins (hereinafter, also referred to as a solid catalyst component, as appropriate) containing magnesium, titanium, a halogen, and an internal electron donor compound. In such polymerization methods, olefins are polymerized in the presence of an olefin polymerization catalyst containing an organoaluminum compound, a silicon compound, and the like, together with the solid catalyst component for polymerizing olefins (see, for example, Patent Document 1).

[0003] Since the polymerization of olefins is carried out continuously industrially, it is important to carry out stable operation, but on the other hand, when a continuous polymerization operation is carried out, the polymer particles produced tend to adhere to the polymerization vessel, piping, etc., and cause piping blockage, etc. Such piping blockage, etc., is thought to be caused by the adhesion of fine powder-like polymer particles (hereinafter also referred to as polymer, as appropriate) which have a large specific surface area and a high electrostatic charge rate, or by the adhesiveness of the polymer particles themselves (stickiness of the particles).

[0004] For example, as described in Patent Document 1, when olefins are polymerized using a polymerization catalyst containing a highly active solid catalyst component and an external electron donor such as an organoaluminum compound and a silicon compound, the resulting polymer tends to contain a large amount of fine powder and have a broad particle size distribution due to the breakdown of polymer particles caused by fine powder of the solid catalyst component itself and the reaction heat during polymerization.

[0005] A broad particle size distribution ultimately has an undesirable effect on the molding and processing of the polymer, so there has been a demand for polymers with fewer fine powder-like polymer particles, a narrow particle size distribution, and uniform particle sizes.

[0006] Furthermore, the copolymer particles obtained by polymerizing the above-mentioned olefins tend to have a sticky surface, which not only makes them difficult to handle and process, but also reduces their flowability due to the stickiness, hindering easy and rapid transportation, and making them prone to causing significant production losses due to pipe blockages. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 1-315406 Summary of the Invention [Problem to be solved by the invention]

[0008] Under these circumstances, the present invention aims to provide a solid catalyst component for olefin polymerization which, when subjected to the polymerization of olefins, can produce polymer particles with a reduced content of fine powder and reduced surface stickiness under high activity, and also to provide a method for producing the solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for producing olefin polymer particles, and olefin polymer particles. [Means for solving the problem]

[0009] A polymer obtained by polymerizing a monomer such as propylene and a solid catalyst component for olefin polymerization that constitutes a catalyst for polymerizing such a monomer (hereinafter also referred to as a catalyst or catalyst particles, as appropriate) have a close relationship. Conventionally, studies have been conducted on the temperature during synthesis and the halogenated substance to be used as a method for synthesizing the solid catalyst component.

[0010] The fine powder polymer particles are thought to be generated due to the fine powder catalyst particles (or the fine powder solid catalyst component for olefin polymerization that constitutes the fine powder catalyst particles) originally contained in the catalyst, or catalyst particles that have been broken down and turned into fine powder during polymerization.

[0011] For this reason, the present inventors first came up with the idea of ​​providing catalyst particles that (1) reduce the content of fine powder catalyst particles that are originally mixed in at a certain rate, and (2) have a structure that is high in strength and will not be destroyed during polymerization.

[0012] Furthermore, it is believed that the stickiness of the polymer particle surface occurs in the case of homopolymerization because olefins, organic solvents, etc. used during polymerization remain in or near the pores on the surface of the polymer particles, and in the case of copolymerization, it occurs as a result of the produced rubber components seeping out onto the surface of the polymer particles.

[0013] Here, since it is believed that the pores formed on the surface of the polymer particles of the above-mentioned homopolymers, copolymers, etc. are formed due to the surface shape of the catalyst particles, the present inventors came up with the idea of ​​(3) providing catalyst particles having a structure that makes it difficult for olefins and rubber components to adhere to the surface or exude.

[0014] In order to provide catalyst particles having the above properties (1) to (3), the present inventors have focused on the internal structure of the solid catalyst component for olefin polymerization constituting the catalyst particles, in particular the relationship with the cross-sectional pore area ratio inside the solid catalyst component for olefin polymerization. That is, the present inventors have focused on the fact that by adopting a solid catalyst component for olefin polymerization having high strength in which the internal cross-sectional pore area ratio (pore area ratio in the cross section of the solid catalyst component particle) and pore distribution are controlled within a predetermined range, it is possible to reduce the amount of fine powder contained in the solid catalyst component for olefin polymerization and further reduce the amount of fine powder contained in the catalyst, to prevent destruction during polymerization and generation of fine powder, and to produce polymer particles in which olefins and rubber components are less likely to adhere to or exude from the surface and have reduced surface stickiness.

[0015] On the other hand, in order to materialize the above idea, it was necessary not only to prepare a solid catalyst component for olefin polymerization having a controlled cross-sectional pore area ratio, but also to develop a method for measuring the internal structure of the obtained solid catalyst component for olefin polymerization.

[0016] That is, since the solid catalyst component for olefin polymerization, which is mainly composed of magnesium, is anaerobic and water-repellent, when particles of the solid catalyst component are cut to be used as measurement samples for analyzing internal information, various types of damage are likely to occur on the cut surface, making it extremely difficult to accurately examine the internal structure of the solid catalyst component for olefin polymerization.

[0017] Conventionally, as a method for obtaining internal information of a solid catalyst component for olefin polymerization, specific surface area measurement and pore size distribution measurement by a gas adsorption method have been known. In this method, gas molecules having a known adsorption area per unit amount are adsorbed onto the surface of a particle to be measured, and the specific surface area of ​​the particle to be measured can be measured from the amount of adsorption, or the pore size distribution can be determined from the condensation of the gas molecules.

[0018] However, although the above method can obtain information about the entire particle, such as the amount of pores inside the particle, more detailed information, such as the pore distribution within the particle, is unknown.

[0019] Another known method is the mercury intrusion method (mercury porosimetry), which takes advantage of the high surface tension of mercury to inject mercury under high pressure into the pores within the particles to be measured, and determines the specific surface area and pore distribution from the pressure applied during pressurization and the amount of mercury injected.However, even with this method, although information about the entire particle, such as the amount of pores inside the particle, can be obtained, more detailed information such as the pore distribution within the particle is unknown.

[0020] Known devices for cutting solid particles include an ion slicer that uses an argon ion beam and a cross-section polisher (CP). However, when cutting solid particles using the above devices, the sample must be embedded in a resin or the like to remove unevenness from the sample surface. However, the inventors' investigations have revealed that particles made of a solid catalyst component for olefin polymerization react with the resin and are altered.

[0021] Furthermore, it was found that if a recess exists in the sample and the sample is cut without being embedded, heat accumulates in the recess, making the sample susceptible to damage such as deformation due to the heat, making precise cross-sectional observation difficult.

[0022] Under these circumstances, the present inventors have discovered that the internal structure of a solid catalyst component for olefin polymerization, which is an anaerobic, water-restrictive particle, can be measured by cutting the component using an air-non-exposed cooled cross-section polisher (a cooled cross-section polisher (CCP)) under an inert atmosphere at a temperature of −70° C. or lower, and have thus completed the present invention.

[0023] That is, the solid catalyst component for olefin polymerization contains magnesium, titanium, a halogen, and an internal electron donor compound, and when the solid catalyst component is cut at a temperature of -70°C or lower using a cooling cross-section processing device that is not exposed to the atmosphere, the cross-sectional pore area ratio (pore area ratio in the particle cross section of the solid catalyst component for olefin polymerization) is 10 to 50%, and the cross-sectional pore area ratio (MX s ) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s The present inventors have found that the above technical problems can be solved by using a solid catalyst component for olefin polymerization in which the ratio is 0.50 to 2.00, and have completed the present invention based on this finding.

[0024] That is, the present invention is (1) Contains magnesium, titanium, halogens, and internal electron donor compounds; The cross-sectional pore area ratio is 10 to 50%; The cross-sectional pore area ratio (MX s ) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s is 0.50 to 2.00 A solid catalyst component for olefin polymerization, (2) A precursor is prepared by contacting a magnesium compound, a tetravalent titanium halide compound, and an internal electron donor compound with each other and applying pressure to the resulting mixture, and then the precursor is further contacted with a tetravalent titanium halide compound and an internal electron donor compound. a method for producing a solid catalyst component for olefin polymerization, (3) (A) the solid catalyst component for olefin polymerization described in (1) above; (B) an organoaluminum compound; A catalyst for olefin polymerization, comprising: (4) The catalyst for olefin polymerization according to (3) above, further comprising (C) an external electron donor compound. (5) A method for producing olefin polymer particles, which comprises polymerizing olefins using the catalyst for olefin polymerization described in either (3) or (4) above. (6) The cross-sectional pore area ratio is 10 to 50%; The cross-sectional pore area ratio (M'X) of the region 50% or more in the radial direction from the particle center s ) to the cross-sectional pore area ratio (M'X i ) ratio M'X i / M'X s is 0.50 to 2.00 Olefin polymer particles characterized by This provides: [Effects of the Invention]

[0025] According to the present invention, there is provided a solid catalyst component for olefin polymerization which, when subjected to the polymerization of olefins, can suitably produce polymer particles having a reduced content of fine powder and reduced surface stickiness under high activity, and there are also provided a method for producing the solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for producing olefin polymer particles, and olefin polymer particles. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 shows an example of a scanning electron microscope (SEM) photograph of the cross section (processed part of the particle cross section) of a measurement particle processed using a non-exposed-to-air cooled cross sectioning device. [Figure 2] This is an example of an SEM image of only the cross section of a particle. [Figure 3] FIG. 1 is a diagram illustrating a method for calculating the area of ​​a particle cross section (the number of pixels constituting the entire particle cross section). [Figure 4] This is a two-tone cross-sectional image of a particle. [Figure 5] FIG. 10 is a diagram illustrating a method for obtaining an image in which the entire cross-section of a particle is displayed in black. [Figure 6] This is a cross-sectional image in which the entire cross-section of the particle is displayed in black. [Figure 7] FIG. 10 is a diagram illustrating a method for identifying a particle center. [Figure 8] FIG. 1 is a diagram illustrating a method for calculating the cross-sectional pore area ratio of a particle's internal region that is less than 50% in the radial direction. [Figure 9] The image shows a two-tone image of the entire particle cross section (left) and an image of the particle's internal region (center of the cross section) covering less than 50% of the particle's cross section in the radial direction. [Figure 10] FIG. 1 is a schematic diagram illustrating a method for evaluating the flowability of a polymer. [Figure 11] 1 is a micrograph showing the dispersion state of EPR in the cross section of a copolymer particle obtained in a comparative example of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0027] First, the solid catalyst component for olefin polymerization according to the present invention will be explained.

[0028] The solid catalyst component for olefin polymerization according to the present invention contains magnesium, titanium, a halogen, and an internal electron donor compound, and has a cross-sectional pore area ratio of 10 to 50%, and a cross-sectional pore area ratio (MX s ) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s is 0.50 to 2.00.

[0029] The solid catalyst component for olefin polymerization of the present invention contains magnesium, titanium, a halogen and an internal electron donor compound.

[0030] The solid catalyst component for olefin polymerization containing magnesium, titanium, a halogen, and an internal electron donor compound can be, for example, a catalyst prepared by contacting a magnesium compound, a tetravalent titanium halide compound, and an internal electron donor compound with each other under pressure, and then contacting the resulting precursor with a tetravalent titanium halide compound and an internal electron donor compound.

[0031] The magnesium compound may be at least one selected from dialkoxymagnesium, magnesium dihalide, alkoxymagnesium halide, and the like.

[0032] Of the above magnesium compounds, dialkoxymagnesium or magnesium dihalide is preferred, and specific examples include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, magnesium dichloride, magnesium dibromide, magnesium diiodide, and the like, with diethoxymagnesium and magnesium dichloride being particularly preferred.

[0033] The dialkoxymagnesium may be one obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.

[0034] The dialkoxymagnesium is preferably in the form of granules or powder, and the shape may be irregular or spherical.

[0035] When a spherical dialkoxymagnesium is used, a polymer powder having a better particle shape (more spherical) and a narrow particle size distribution can be obtained, which improves the handleability of the polymer powder produced during the polymerization operation and makes it possible to suppress the occurrence of blockages and the like due to fine particles contained in the produced polymer powder.

[0036] The spherical dialkoxymagnesium does not necessarily have to be perfectly spherical, and ellipsoidal or potato-shaped ones can also be used.

[0037] The average particle diameter of the dialkoxy magnesium is measured using a laser light scattering diffraction particle size measuring instrument. 50 The particle size (50% particle size in terms of cumulative particle size in volume cumulative particle size distribution) is preferably 1 to 500 μm, more preferably 10 to 250 μm, and even more preferably 10 to 100 μm.

[0038] When the dialkoxy magnesium is spherical, the average particle diameter D 50 The thickness is preferably 1 to 100 μm, more preferably 5 to 80 μm, and even more preferably 10 to 60 μm.

[0039] The particle size of the dialkoxy magnesium is preferably such that the content of fine particles and coarse particles is small and the particle size distribution is narrow.

[0040] Specifically, when measured using a laser light scattering diffraction particle size analyzer, the dialkoxymagnesium preferably contains 20% by mass or less of particles having a size of 10 μm or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.On the other hand, when measured using a laser light scattering diffraction particle size analyzer, the dialkoxymagnesium preferably contains 10% by mass or less of particles having a size of 100 μm or more, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0041] Furthermore, the following formula (D 90 -D 10 ) / D 50 The particle size distribution SPAN calculated by the above formula is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. 90 is the particle size of 90% of the cumulative particle size in the volume cumulative particle size distribution measured using a laser light scattering diffraction particle size analyzer, D 10 is the particle size of 10% of the cumulative particle size in the volume cumulative particle size distribution measured using a laser light scattering diffraction particle size analyzer.

[0042] By using the dialkoxymagnesium in which the amount of fine powder and the like are controlled as described above and the particle size distribution (SPAN) is controlled within the above range, it is possible to easily provide a solid catalyst for olefin polymerization that can produce polymer particles with a reduced content of fine powder under high activity.

[0043] Furthermore, the bulk density of the dialkoxymagnesium is preferably 0.20 to 0.40 g / ml, more preferably 0.23 to 0.37 g / ml, and even more preferably 0.25 to 0.35 g / ml.

[0044] In the present application, the bulk density of the dialkoxymagnesium refers to the value measured according to the standard of JIS K6721 (1977).

[0045] When the bulk density of the dialkoxymagnesium is within the above range, it is possible to easily provide a solid catalyst for olefin polymerization that can produce polymer particles with a reduced content of fine powder under high activity.

[0046] Methods for producing the dialkoxymagnesium are exemplified in, for example, JP-B 03-074341, JP-A 2013-095890, WO 2013 / 058193, etc.

[0047] The magnesium compound is preferably in the form of a suspension during the reaction, and being in the form of a suspension allows the reaction to proceed favorably.

[0048] When the magnesium compound is a solid, it can be suspended in a solvent that does not have the ability to solubilize the magnesium compound to form a magnesium compound suspension.

[0049] The medium that does not have the ability to solubilize a solid magnesium compound may be one or more solvents selected from saturated hydrocarbon solvents and unsaturated hydrocarbon solvents that do not dissolve the magnesium compound.

[0050] The tetravalent titanium halide compound constituting the solid catalyst component for olefin polymerization according to the present invention is not particularly limited, but may be any of the following general formula (I): Ti(OR 1 ) r X 4-r (I) (In the formula, R 1 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, r is 0 or an integer of 1 to 3, and R 1 Or if there are multiple Xs, each R 1 or X may be the same or different), it is preferable that the compound is one or more compounds selected from the group consisting of titanium halides and alkoxy titanium halides represented by the formula (I)

[0051] Examples of titanium halides include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.

[0052] Examples of the alkoxytitanium halide include at least one selected from methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride.

[0053] As the tetravalent titanium halide compound, titanium tetrahalide is preferred, and titanium tetrachloride is more preferred.

[0054] These titanium compounds can be used alone or in combination of two or more.

[0055] The internal electron donor compound constituting the solid catalyst component is not particularly limited, but is preferably an organic compound containing an oxygen atom or a nitrogen atom, and examples thereof include one or more compounds selected from alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, and organosilicon compounds containing a Si-O-C bond or a Si-N-C bond.

[0056] The internal electron donor compound is more preferably an ether compound such as a monoether, a diether, or an ether carbonate, or an ester such as a monocarboxylic acid ester or a polycarboxylic acid ester, and even more preferably at least one selected from aromatic polycarboxylic acid esters such as an aromatic dicarboxylic acid diester, aliphatic polycarboxylic acid esters such as a saturated aliphatic polycarboxylic acid ester or an unsaturated aliphatic polycarboxylic acid ester, an alicyclic polycarboxylic acid ester, a diether, or an ether carbonate.

[0057] Examples of the internal electron donor compound include, in particular, di-n-butyl phthalate, di-n-propyl phthalate, diethyl phthalate, diethyl maleate, dibutyl maleate, dibutyl dimethyl maleate, dibutyl diethyl maleate, diethyl diisobutyl maleate, diethyl succinate, diethyl methyl succinate, diethyl 2,3-diisopropyl succinate, di-n-butyl malonate, diethyl malonate, dimethyl diisobutyl malonate, and diisobutyl methyl succinate. Preferred are one or more selected from the group consisting of diethyl malonate, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, (2-ethoxyethyl)ethyl carbonate, (2-ethoxyethyl)phenyl carbonate, dimethyl benzylidenemalonate, diethyl benzylidenemalonate, and dibutyl benzylidenemalonate.

[0058] Details of the conditions for preparing a precursor by contacting the magnesium compound, tetravalent titanium halide compound, and internal electron donor compound with each other and applying pressure, as well as the conditions for further contacting the obtained precursor with the tetravalent titanium halide compound and the internal electron donor compound, are as described later in the description of the method for producing a solid catalyst component for olefin polymerization according to the present invention.

[0059] In the solid catalyst component for olefin polymerization according to the present invention, the magnesium atom content is preferably 10 to 70 mass %, more preferably 10 to 50 mass %, further preferably 15 to 40 mass %, particularly preferably 15 to 25 mass %.

[0060] In the solid catalyst component for olefin polymerization according to the present invention, the content of titanium atoms is preferably from 0.5 to 8.0 mass %, more preferably from 0.5 to 5.0 mass %, and further preferably from 0.5 to 3.5 mass %.

[0061] In the solid catalyst component for olefin polymerization according to the present invention, the content of halogen atoms is preferably 20 to 88 mass %, more preferably 30 to 85 mass %, even more preferably 40 to 80 mass %, and still more preferably 45 to 75 mass %.

[0062] In the solid catalyst component for olefin polymerization according to the present invention, the content of the internal electron donor compound is preferably from 1.5 to 30 mass %, more preferably from 3.0 to 25 mass %, and even more preferably from 6.0 to 25 mass %.

[0063] In the present application, the content of magnesium atoms in the solid catalyst component means the value measured by the EDTA titration method in which the solid catalyst component is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.

[0064] In the present application, the content of titanium atoms in the solid catalyst component means the value measured in accordance with the method (oxidation-reduction titration) described in JIS 8311-1997 "Method for determining titanium in titanium ore."

[0065] In the present application, the content of halogen atoms in a solid catalyst component means a value measured by a silver nitrate titration method in which the solid catalyst component is treated with a mixed solution of sulfuric acid and pure water to prepare an aqueous solution, a predetermined amount of which is then taken, and the halogen atoms are titrated with a silver nitrate standard solution.

[0066] In the present application, the content of the internal electron donor compound in the solid catalyst component means the result obtained by measuring under the following conditions using a gas chromatograph (GC-14B, manufactured by Shimadzu Corporation) using a calibration curve measured in advance based on known concentrations. <Measurement conditions> Column: Packed column (φ2.6 × 2.1 m, Silicone SE-30 10%, Chromosorb WAWDMCS 80 / 100, GL Sciences Inc.) Detector: FID (Flame Ionization Detector) Carrier gas: Helium, flow rate 40 ml / min Measurement temperature: Vaporizer 280°C, column 225°C, detector 280°C, or vaporizer 265°C, column 180°C, detector 265°C

[0067] The solid catalyst component for olefin polymerization according to the present invention has a cross-sectional pore area ratio (pore area ratio in the cross section of the particle of the solid catalyst component for olefin polymerization) of 10 to 50%, preferably 20 to 50%, more preferably 20 to 45%, and even more preferably 25 to 40%.

[0068] In addition, the solid catalyst component for olefin polymerization according to the present invention has a cross-sectional pore area ratio (MX s ) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s is 0.50 to 2.00, preferably 0.80 to 2.00, more preferably 1.00 to 2.00, and even more preferably 1.00 to 1.50.

[0069] In this application, the center of a particle means the intersection point (intersection point O in Figures 7(a) and 7(b)) when a cross-sectional image of any particle is placed within a rectangle (or square) and perpendicular lines are drawn from the midpoints of two adjacent sides, as illustrated in Figure 7(a) or 7(b).

[0070] In addition, in the present application documents, a region that is 50% or more in the radial direction from the particle center means, in the cross section of the particle to be measured, the region that is located on and outside the boundary line with the reduced image when (i) the pixel dimensions (the width and height values ​​of the observed image) are each reduced to 1 / 2, and (ii) an image obtained by restoring only the number of pixels of the observed image to the original value is pasted on top of the original image; and a region that is less than 50% in the radial direction means the region that is located inside the boundary line with the reduced image when (i) the pixel dimensions (the width and height values ​​of the observed image) are each reduced to 1 / 2, and (ii) an image obtained by restoring only the number of pixels of the observed image to the original value is pasted on top of the original image.

[0071] Specifically, first, (i) as shown in Figure 8(a) below, an observation image is read in which the entire particle area is filled in black, and the pixel dimensions of the image (the numerical values ​​of the image width and height) are read and recorded. Then, as shown in Figure 8(b), the pixel dimensions of the width and height are each reduced to 1 / 2. Next, (ii) as shown in Figure 8(c), only the number of pixels in the image is restored to the original value, and the entire image is copied. After that, as shown in Figure 8(d), the two-tone image shown in Figure 8(a) is loaded. As shown in Figure 8(e), the image of Figure 8(c) previously copied is pasted as a separate layer on the two-tone image shown in Figure 8(d) (so that the particle centers coincide). In this case, in the example of Figure 8(e), the center part is filled in black and the periphery is displayed as black dots. The periphery (including the boundary line with the center) displayed as black dots corresponds to an area of ​​50% or more in the radial direction, and the center part (excluding the boundary line with the periphery) corresponds to an area of ​​less than 50% in the radial direction.

[0072] The morphology of the solid catalyst component for olefin polymerization according to the present invention is preferably spherical from the viewpoint of ease of measurement, but since the peripheral portion of the particle cross section is cut out in the subsequent analysis, even if the solid catalyst component for olefin polymerization is spherical or irregular in shape, no problem occurs in measurement. sand average pore area ratio MX i / MX s It is believed that by using a solid catalyst component for olefin polymerization having the above formula, it is possible to produce polymer particles with a reduced content of fine powder and reduced surface stickiness under high activity.

[0073] That is, because the reaction of a catalyst for olefin polymerization is a surface reaction, if there are many pores near the catalyst surface during olefin polymerization, reaction heat is likely to accumulate, resulting in an explosive reaction and the generation of fine polymer particles. Conversely, if there are fewer pores near the surface of the solid catalyst component, there is less heat accumulation, reducing the reaction heat, and as a result, it is thought that the generation of fine powdery polymer is suppressed.

[0074] Therefore, in the present invention, the solid catalyst component for olefin polymerization has the above cross-sectional pore area ratio and average pore area ratio MX i / MX s It is considered that the use of a solid catalyst having the above formula (I) can easily provide a solid catalyst for olefin polymerization which, when subjected to the polymerization of olefins, can produce polymer particles with a suppressed content of fine powder and reduced surface stickiness under high activity.

[0075] In the present application, the cross-sectional pore area ratio and the average pore area ratio MX of the solid catalyst component for olefin polymerization according to the present invention are i / MX s means the value at the cross section when a gold coating is formed as a thermally conductive coating on the surface of a solid catalyst component for olefin polymerization by physical vapor deposition (PVD), and the cross section is cut using a cooled cross section polisher (CCP) that is not exposed to the atmosphere, under a temperature condition of -70°C or lower, preferably -110°C or lower.

[0076] The details of the method for cutting and processing the solid catalyst component are as follows.

[0077] First, solid catalyst component particles for olefin polymerization attached to a solid (substrate) are placed in a sealed chamber, and gold, which is the film-forming substance (target), is evaporated at high temperature in a nitrogen gas atmosphere and attached to the surface of the solid catalyst component particles for olefin polymerization, forming a gold thin film by physical vapor deposition (PVD).

[0078] In the present application, the gold thin film refers to a film formed by the following method. That is, an ion sputter (JFC-1600, manufactured by JEOL Ltd.) equipped with a gold target for deposition and a rotating stage is placed in a glove box for deposition work that has been thoroughly purged with nitrogen, and the solid catalyst component, a spatula, an aluminum shallow container, and a silicon wafer (5 mm long x 10 mm wide x 0.2 mm thick) with conductive double-sided tape previously attached are placed in the glove box. After thoroughly purging the inside of the glove box with nitrogen, a plastic shallow container containing approximately 500 mg of the solid catalyst component is set in the ion sputter, and gold deposition is carried out for 3 to 15 minutes while rotating the stage at a speed of 30 rpm under conditions of an ultimate vacuum of 15 Pa or less and an applied current of 20 to 40 mA. This means the formation of a gold thin film.

[0079] By providing a gold coating on the surface, not only can contact with moisture and oxygen in the air be reduced, but charging by high-temperature plasma during the cutting process described below can also be easily suppressed, preventing melting of the processed surface and enabling accurate analysis of its internal structure.

[0080] Next, the solid catalyst component particles for olefin polymerization having the gold coating on the surface were scattered and fixed on the surface of a conductive double-sided tape attached to a silicon wafer so that the particles did not overlap each other, and then polished for 10 minutes using a non-exposed-to-air cooled cross-section polisher (cooled cross-section polisher (CCP)) manufactured by JEOL Ltd., IB-19520CCP. -3 The cutting process is carried out in a vacuum atmosphere of 100 Pa or less at a temperature of -70°C or less, preferably -110°C or less.

[0081] When irradiating the solid catalyst component particles with an argon beam, the argon ion beam may be continuously applied until cross-section processing is completed, but cross-section processing can also be performed by turning the argon beam on and off for a certain period of time, i.e., by so-called intermittent measurement.

[0082] By carrying out cross-section processing under the above temperature conditions, it is possible to carry out cross-section processing with high accuracy while suppressing thermal damage to the particles of the solid catalyst component for olefin polymerization.

[0083] Next, a scanning electron microscope (SEM) JSM-F100 manufactured by JEOL Ltd. is used, and the cross-section processed solid catalyst component particles for olefin polymerization are set together with the transfer vessel removed from the CCP cross-section processing device, and a backscattered electron image of the cross-section processed portion is observed.

[0084] After setting the threshold, a binary image of only the particle surface (flat surface) is created to obtain the desired surface observation image.

[0085] Figure 1 shows an example of a surface observation image of the cross-section processed part of a particle observed in this way.

[0086] In the cross section of the particle shown in FIG. 1, the white areas indicate textured areas (flat areas), and the black areas indicate pore areas (recessed areas).

[0087] In the solid catalyst component for olefin polymerization according to the present invention, 500 (500 particles) solid catalyst component particles with processed cross sections were used, and the arithmetic mean values ​​of the cross-sectional pore area ratio, the cross-sectional pore area ratio of a region of 50% or more in the radial direction from the particle center, and the cross-sectional pore area ratio of a region less than 50% in the radial direction were determined by the following methods. These values ​​were referred to as the cross-sectional pore area ratio, the cross-sectional pore area ratio of a region of 50% or more in the radial direction from the particle center (MX s ) and the cross-sectional pore area ratio (MX i ) shall be as follows.

[0088] In the solid catalyst component for olefin polymerization according to the present invention, the cross-sectional pore area ratio, the cross-sectional pore area ratio of a region of 50% or more in the radial direction from the particle center, and the cross-sectional pore area ratio of a region of less than 50% in the radial direction refer to values ​​calculated by the following method using image analysis software (Photoshop manufactured by Adobe) equipped with an image 2-level gradation function, brightness measurement function, and pixel number measurement function in a specified range.

[0089] <Image analysis method> (1) Identifying the image to be analyzed Image analysis software (Adobe Photoshop) is started, and the image of the particle cross section that was taken is read and converted into grayscale (this operation is not necessary if the image is already a monochrome image).

[0090] Next, change the "Foreground and Background Color" setting in the toolbox to "Foreground Color / Background Color = White / Black," then paint the area outside the outline of the particle image white to remove it, and save the image that contains only the particle cross-section, as shown in Figure 2.

[0091] (2) Calculation of the cross-sectional area of ​​the particle (the number of pixels that make up the entire cross-section of the particle) The image of only the cross-section of the particle obtained in (1) is retrieved, and a histogram (as shown in Figure 3) is obtained that shows the distribution of the number of pixels for the darkness (darkness 0 (white) to darkness 255 (black)) of each pixel that makes up the image.

[0092] As shown in FIG. 3, if the histogram obtained has one peak (unimodal), the cursor (indicated by a triangle) on the screen is moved so that the rising portion (inflection point) at the left foot of the peak becomes the threshold value. If the histogram obtained has two or more peaks (multimodal), the rising portion (inflection point) at the left foot of the rightmost peak becomes the threshold value. By moving the cursor (indicated by a triangle) on the screen and converting the peak to two gradations, a two-gradation cross-sectional image of the particle as shown in FIG. 4 is obtained, and the obtained image data is saved.

[0093] On the other hand, as shown in Figure 5, by moving the cursor (shown by a ▲ mark) on the screen to a darkness of 255 (black), an image is obtained in which the entire particle portion is displayed in black, as shown in Figure 6, and the image data is saved.

[0094] Next, the "average" value of darkness (average a) and the "total pixel" number (total pixel a) in the entire observed image are read from the "expanded display" of the histogram in the obtained image data, and the number of white pixels at this time, x, is calculated using the following formula and then rounded to an integer value. x = (average a) × (total number of pixels a) ÷ 255

[0095] Then, the area of ​​the particle cross section ((the number of pixels constituting the entire particle cross section (the number of black pixels)) in the entire observed image exemplified in FIG. 6) is calculated using the following formula. Area of ​​particle cross section (number of pixels constituting the entire particle cross section) = (total number of pixels a) - x

[0096] (3) Calculation of the pore area in the particle cross section (the number of pixels that make up the pore in the particle cross section) The two-tone particle cross-sectional image obtained in (2) shown in Figure 4 is called up, and the "average" value of darkness (average b) and the "total pixel" number (total pixel a) in the entire observed image are read from the "expanded display" of the histogram. The number of white pixels at this time, y, is calculated using the following formula, and then rounded to an integer value. y = (average b) × (total pixels a) ÷ 255

[0097] Then, the pore area (number of black pixels) of the particle cross section in the entire observation image exemplified in FIG. 4 is calculated using the following formula. Pore ​​area in particle cross section (number of pixels constituting the pore in the particle cross section) = (total pixels a) - y

[0098] (4) Calculation of cross-sectional pore area ratio Based on the particle cross-sectional area (the number of pixels constituting the entire particle cross-section) calculated in (2) and (3) above and the pore area in the particle cross-section (the number of pixels constituting the pores in the particle cross-section), the cross-sectional pore area ratio is calculated using the following formula. Cross-sectional pore area ratio (%) = {pore area in particle cross section (number of pixels constituting the pores in the particle cross section) / area of ​​particle cross section (number of pixels constituting the entire particle cross section)} × 100

[0099] In the present application, the arithmetic mean value of the cross-sectional pore area ratios of 500 particles of the solid catalyst component for olefin polymerization determined by the above method is taken as the cross-sectional pore area ratio.

[0100] (5) Calculation of the cross-sectional pore area ratio of the particle internal region (center of particle cross section) less than 50% in the radial direction FIG. 8 is a diagram for explaining a method for calculating the cross-sectional pore area ratio in the particle internal region (the central part of the particle cross section) that is less than 50% in the radial direction.

[0101] As shown in Figure 8(a), an image in which the entire particle area is displayed in black is read, and the pixel dimensions of the image (the numerical values ​​of the image's width and height) are read and recorded.Then, as shown in Figure 8(b), the pixel dimensions of the width and height are each reduced to 1 / 2.Next, as shown in Figure 8(c), only the number of pixels in the image is returned to the original value, and the entire image is copied.

[0102] Then, as shown in Figure 8(d), the two-toned image of the figure shown in Figure 8(a) is read, and then, as shown in Figure 8(e), the image of Figure 8(c) that was copied in advance is pasted on top as a separate layer.

[0103] As shown in Figure 8(f), select the central black area pasted as a separate layer in Figure 8(e), and then invert the selected area as shown in Figure 8(g). In this state, delete the selected area from the lower layer as shown in Figure 8(h), and then delete the entire upper layer as shown in Figure 8(i), thereby obtaining an image in which the area from the center of the particle to 50% in the radial direction is displayed in two tones.

[0104] Using the above method, a cross-sectional image in which the entire particle portion shown in Figure 6 is displayed in black can be obtained from the image shown in the left figure of Figure 9 (the two-tone particle cross-sectional image shown in Figure 4 obtained in (2)), and these cross-sectional images can be used to obtain an image in which the area from the center of the particle to 50% in the radial direction is displayed in two tones, as shown in the right figure of Figure 9.

[0105] In the image data shown on the right in Figure 9, the number of "total pixels" (total pixels c) and the "average" value of darkness (average c) are read from the "expanded display" of the histogram, and the number of white pixels z in the entire observed image at this time is calculated using the following formula, and then rounded to an integer value. z = (average c) × (total pixel c) ÷ 255

[0106] In the image data of the particle internal region (center of cross section) less than 50% in the radial direction in the right diagram of Figure 9, if we assume that the particle cross sections shown in the right and left diagrams of Figure 9 are each perfect circles, the radius of the particle cross section shown in the right diagram of Figure 8 (Figure 8(b)) is half the radius of the particle cross section shown in the left diagram of Figure 9, so mathematically the area of ​​the entire particle cross section (number of black pixels) in the right diagram of Figure 8 is 1 / 4 of the area of ​​the entire particle cross section (number of black pixels) in the entire observation image in the left diagram of Figure 9. Therefore, the pore area (number of black pixels) in the particle internal region (center of particle cross section) less than 50% in the radial direction shown in the right diagram of Figure 9 can be calculated using the following formula. Pore ​​area at the center of particle cross section = [{(total pixels a)-x}×0.25]-z

[0107] The total cross-sectional area of ​​the particle internal region (the center of the particle cross section) less than 50% in the radial direction shown in the right diagram of FIG. 9 can be calculated by the following formula. Total cross-sectional area of ​​the particle's internal region (center of particle cross section) less than 50% in the radial direction = {(total number of pixels a) - x} × 0.25

[0108] Therefore, the cross-sectional pore area ratio (MX i ) can be calculated using the following formula: The cross-sectional pore area ratio (MX) of the particle internal region (center of particle cross section) less than 50% in the radial direction i ) (%) = (pore area at the center of particle cross section / total cross-sectional area at the center of particle cross section) × 100

[0109] (6) Calculation of the cross-sectional pore area ratio of the surface near-surface region (edge ​​of particle cross section) of 50% or more in the radial direction The total area (number of black pixels) of the near-surface region (periphery of the particle cross section) that is 50% or more in the radial direction is 3 / 4 of the total cross-sectional area of ​​the particle (number of black pixels) in the entire observation image in Figure 9, for the same reasons as those described in (5) above for calculating the total cross-sectional area of ​​the particle's internal region (center of the particle cross section) that is less than 50% in the radial direction. Therefore, the total area of ​​the near-surface region (periphery of the particle cross section) that is 50% or more in the radial direction can be calculated using the following formula. Total area at the edge of particle cross section = [{(total pixels a)-x} × 0.75]

[0110] The total pore area in a region near the surface (periphery of the particle cross section) that is 50% or more in the radial direction can be calculated by the following formula. Pore ​​area at the periphery of particle cross section = (pore area of ​​entire particle cross section) - (pore area at the center of particle cross section)

[0111] Therefore, the cross-sectional pore area ratio (MX s ) can be calculated using the following formula: The cross-sectional pore area ratio (MX) of the surface near-surface region (edge ​​of particle cross section) of 50% or more in the radial direction s ) (%) = {pore area at the periphery of the particle cross section / total area at the periphery of the particle cross section} × 100

[0112] (7) Cross-sectional pore area ratio (MX s ) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s Calculation of The arithmetic average value of the cross-sectional pore area ratio of the surface region of 50% or more in the radial direction of 500 particles of the solid catalyst component for olefin polymerization obtained by the above method was defined as the cross-sectional pore area ratio of the region of 50% or more in the radial direction (MX s ) and the arithmetic average value of the cross-sectional pore area ratios of the particle internal regions less than 50% in the radial direction of 500 particles of the solid catalyst component for olefin polymerization determined by the above method was defined as the cross-sectional pore area ratio (MX i ) and then calculate the cross-sectional pore area ratio (MX s ) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s can be calculated.

[0113] The solid catalyst component for olefin polymerization according to the present invention may contain 5 to 20 mass % of a liquid hydrocarbon compound.

[0114] The hydrocarbon compound may be a compound represented by the general formula C n H (2n+2) (wherein n is an integer of 5 to 20).

[0115] The "liquid hydrocarbon compound" according to this embodiment refers to a compound that is liquid at room temperature and has a boiling point of 50 to 150° C. Examples of the hydrocarbon compound represented by the general formula (I) above include one or more compounds selected from pentane, hexane, heptane, octane, nonane, decane, dodecane, tridecane, pentadecane, icosane, mineral oil (liquid paraffin), and the like.

[0116] The content of liquid hydrocarbons contained in the solid catalyst component for olefin polymerization according to the present invention can be calculated by taking about 10 g of the solid catalyst component under a nitrogen atmosphere into a 100 ml recovery flask that has been previously purged with nitrogen and whose empty mass has been measured, recording the weighed value M (g), and then drying under reduced pressure at 50°C or higher for 2 hours or more using a vacuum pump (manufactured by ULVAC, Inc., model number G-100D) although this depends on the boiling point of the hydrocarbon. After cooling to room temperature, the pressure inside the recovery flask is returned to normal pressure with nitrogen gas, and then measuring the weighed value N (g) of the reduced-pressure dried product, and then using the following formula: Liquid hydrocarbon content in the solid catalyst component (mass%) = [{M(g) - N(g)} / M(g)] × 100

[0117] The solid catalyst component for olefin polymerization according to the present invention can contain, for example, the liquid hydrocarbon in its internal pores.

[0118] When the solid catalyst component for olefin polymerization according to the present invention contains a liquid hydrocarbon, the cross-sectional pore area ratio and the average pore area ratio MX of the solid catalyst component for olefin polymerization according to the present invention described above can be i / MX s is determined by cutting the specimen with a non-exposed-to-air cooled cross-section processing device (cooled cross-section polisher (CCP)), cleaning the specimen, and then observing the surface with the SEM.

[0119] The above-mentioned washing treatment method can be carried out by removing the liquid hydrocarbons by drying under reduced pressure using a vacuum pump (ULVAC, Model No. G-100D) or by flash drying in a nitrogen atmosphere if the liquid hydrocarbon is hexane, heptane, or the like having a boiling point of 100°C or less; and by allowing a small amount of hexane or heptane to flow down onto the cross section of the solid catalyst component particles after cutting, followed by drying under reduced pressure using a vacuum pump (ULVAC, Model No. G-100D) or by flash drying in a nitrogen atmosphere if the liquid hydrocarbon is decane, dodecane, or the like having a boiling point higher than 100°C.

[0120] According to the present invention, it is possible to provide a solid catalyst component for olefin polymerization which, when subjected to the polymerization of olefins, can produce polymer particles with a reduced content of fine powder and reduced surface stickiness under high activity. The solid catalyst component for olefin polymerization according to the present invention can be suitably prepared by the production method according to the present invention, which will be explained below.

[0121] Next, the method for producing the solid catalyst component for olefin polymerization according to the present invention will be described. The method for producing a solid catalyst component for olefin polymerization according to the present invention is characterized in that a precursor is prepared by contacting a magnesium compound, a tetravalent titanium halide compound, and an internal electron donor compound with each other and applying pressure thereto, and then further contacting the precursor with a tetravalent titanium halide compound and an internal electron donor compound with each other. The method for producing a solid catalyst component for olefin polymerization according to the present invention can also be expressed as comprising: a precursor preparation step in which a magnesium compound, a tetravalent titanium halide compound, and an internal electron donor compound are brought into contact with each other and pressurized to prepare a precursor; and a main preparation step in which the precursor obtained in the precursor preparation step is further brought into contact with a tetravalent titanium halide compound and an internal electron donor compound.

[0122] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, specific examples of the magnesium compound used in producing the precursor include those similar to those mentioned above, and specific examples of the tetravalent titanium halide compound and internal electron donor compound used in producing the precursor include those similar to those mentioned above.

[0123] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, the precursor is preferably one obtained by mixing a magnesium compound, a tetravalent titanium halide compound, and an internal electron donor compound under pressure in an inert gas atmosphere and in the presence of an appropriate inert organic solvent, thereby contacting and reacting them.

[0124] The amount of the tetravalent titanium halide compound to be catalytically reacted per mole of the magnesium compound is preferably 0.5 to 100 moles, more preferably 0.5 to 50 moles, and even more preferably 1 to 10 moles.

[0125] The amount of the internal electron donor compound to be catalytically reacted per mole of the magnesium compound is preferably 0.01 to 10 moles, more preferably 0.01 to 1 mole, and even more preferably 0.02 to 0.6 moles.

[0126] When the magnesium compound, the tetravalent titanium halide compound, and the internal electron donor compound are brought into contact with each other, the tetravalent titanium halide compound and the internal electron donor compound may be contacted in a state where they have previously formed a complex.

[0127] The complex of the tetravalent titanium halide compound and the internal electron donor compound is preferably one in which the catalytic reaction amount of the internal electron donor compound per mole of the tetravalent titanium halide compound is 0.5 moles, 1 mole, or 2 moles, more preferably 1 mole.

[0128] The amount of the complex of the tetravalent titanium halide compound and the internal electron donor compound to be catalytically reacted per mole of the magnesium compound is preferably 5 to 200 moles, more preferably 20 to 150 moles.

[0129] Furthermore, when an inert organic solvent is used, a saturated or unsaturated hydrocarbon solvent that does not readily dissolve the magnesium compound is preferred. Specific examples of such an inert organic solvent, due to their high safety and industrial versatility, include linear or branched aliphatic hydrocarbon compounds having a boiling point of 50 to 200°C selected from hexane, heptane, decane, methylheptane, etc.; alicyclic hydrocarbon compounds having a boiling point of 50 to 200°C selected from cyclohexane, ethylcyclohexane, decahydronaphthalene, etc.; and aromatic hydrocarbon compounds having a boiling point of 50 to 200°C selected from toluene, xylene, ethylbenzene, etc., among which linear aliphatic hydrocarbon compounds having a boiling point of 50 to 200°C selected from hexane, heptane, decane, etc. and aromatic hydrocarbon compounds having a boiling point of 50 to 200°C selected from toluene, xylene, ethylbenzene, etc., are preferred. These solvents may be used alone or in combination.

[0130] The amount of the inert organic solvent used per mole of the magnesium compound is preferably 0.001 to 500 moles, more preferably 0.5 to 100 moles, and even more preferably 1.0 to 20 moles.

[0131] The temperature during contact and reaction of the magnesium compound, tetravalent titanium halide compound, and internal electron donor compound is preferably 20 to 105° C., more preferably 20 to 100° C., and even more preferably 25 to 90° C. The reaction time is preferably 1 to 240 minutes, more preferably 1 to 180 minutes, and even more preferably 30 to 180 minutes.

[0132] The inert gas constituting the inert gas atmosphere during the contact and reaction of the magnesium compound, tetravalent titanium halide compound, and internal electron donor compound can be one or more selected from nitrogen gas, helium gas, neon gas, argon gas, krypton gas, xenon gas, etc., and from the viewpoint of cost, nitrogen gas or argon gas is preferred, with nitrogen gas being more preferred.

[0133] The pressure (gauge pressure) applied during contact and reaction of the magnesium compound, tetravalent titanium halide compound, and internal electron donor compound is preferably 0.01 to 0.9 MPa, more preferably 0.11 to 0.9 MPa.

[0134] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, the precursor is prepared by contacting and reacting the magnesium compound, the tetravalent titanium halide compound, and the internal electron donor compound under an inert gas atmosphere and under pressure, thereby suppressing the generation of fine powdery solid catalyst component particles that are a cause of the generation of fine powdery polymer particles, and further changing the structure of the resulting solid catalyst component to give a solid catalyst component superior in strength compared to a product obtained by contact and reaction under no pressure.

[0135] In preparing the precursor, the contact and reaction of the magnesium compound, tetravalent titanium halide compound, and internal electron donor compound can be carried out, for example, by charging the magnesium compound, tetravalent titanium halide compound, and internal electron donor compound, and optionally an inert organic solvent, into an autoclave that is filled with an inert gas and can be pressurized under conditions where moisture and the like have been removed, and then pressurizing the interior of the autoclave while stirring with a stirrer.

[0136] The obtained precursor preferably has a cross-sectional pore area ratio (pore area ratio in the precursor particle cross section) of 10 to 50%, more preferably 20 to 50%, even more preferably 20 to 45%, and particularly preferably 25 to 40%.

[0137] The obtained precursor has a cross-sectional pore area ratio (M''X) of 50% or more in the radial direction from the particle center. s ) to the cross-sectional pore area porosity (M''X i ) ratio M''X i / M''X sis preferably 0.50 to 2.00, more preferably 0.80 to 2.00, further preferably 1.00 to 2.00, and particularly preferably 1.00 to 1.50.

[0138] In the present invention, the precursor has the above cross-sectional pore area ratio and average pore area ratio M″X i / M''X s It is believed that the use of a catalyst having the above formula (I) can easily provide a solid catalyst for olefin polymerization that can produce polymer particles with a reduced content of fine powder and reduced surface stickiness under high activity.

[0139] That is, since the reaction of a catalyst for olefin polymerization is a surface reaction, if there are many pores near the catalyst surface during olefin polymerization, reaction heat is likely to accumulate, resulting in an explosive reaction and the generation of fine polymer particles. Conversely, if there are fewer pores near the surface of the solid catalyst component, there is less heat accumulation, reducing the reaction heat, and as a result, it is thought that the generation of fine powdery polymer is suppressed.

[0140] In the present application, the cross-sectional pore area ratio of the precursor and the cross-sectional pore area ratio (M″X s ) to the cross-sectional pore area ratio (M''X i ) ratio M''X i / M''X s Each of the values ​​means a value on a cut surface of a precursor when the precursor is provided with a thermally conductive coating on its surface and cut using a non-air-exposed cooled cross-section processing device under a temperature condition of −70° C. or lower, and the details of the cutting method are the same as those of the above-mentioned cutting method of the solid catalyst component for olefin polymerization according to the present invention.

[0141] In addition, the cross-sectional pore area ratio and M''X of the precursor i / M''X s is the cross-sectional pore area ratio of the solid catalyst component for olefin polymerization according to the present invention and the cross-sectional pore area ratio of the region of 50% or more in the radial direction (MX s) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s The value is measured in the same manner as above. In the precursor, 500 precursor particles (500 particles) were cut and processed by the method described above, and the arithmetic mean values ​​of the cross-sectional pore area ratio, the cross-sectional pore area ratio of a region at least 50% in the radial direction from the particle center, and the cross-sectional pore area ratio of a region less than 50% in the radial direction, which were determined by the same method as described above, were respectively referred to as the cross-sectional pore area ratio, the cross-sectional pore area ratio of a region at least 50% in the radial direction from the particle center (M''X s ) and the cross-sectional pore area ratio of the region less than 50% in the radial direction (M''X i ) shall be as follows.

[0142] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, the precursor is further subjected to a main preparation step of contacting a tetravalent titanium halide compound and an internal electron donor compound to prepare a solid catalyst component for olefin polymerization.

[0143] Specific examples of the tetravalent titanium halide compound and internal electron donor compound to be brought into contact with the precursor in this preparation step include those mentioned above, and may be the same as or different from the tetravalent titanium halide compound and internal electron donor compound used in the precursor preparation step.

[0144] In this preparation step, the contact reaction of the precursor with the tetravalent titanium halide compound and the internal electron donor compound is preferably carried out in an inert gas atmosphere, which may be the same as that used in the above-mentioned preparation step of the precursor.

[0145] The amount of the precursor and the tetravalent titanium halide compound to be catalytically reacted is preferably 0.5 to 100 mol, more preferably 0.5 to 50 mol, and even more preferably 1 to 10 mol per 1 mol of the magnesium compound in the precursor.

[0146] The amount of the precursor and the internal electron donor compound that undergoes contact reaction is preferably 0.01 to 10 mol, more preferably 0.01 to 1 mol, and even more preferably 0.02 to 0.6 mol per mol of the magnesium compound in the precursor.

[0147] Furthermore, the contact reaction of the precursor with the tetravalent titanium halide compound and the internal electron donor compound in this preparation step may be carried out in the presence of an inert organic solvent. When an inert organic solvent is used, the amount of the inert organic solvent used per mole of the magnesium compound is preferably 0.001 to 500 moles, more preferably 0.5 to 100 moles, and even more preferably 1.0 to 20 moles. Specific examples of the inert organic solvent include those used in the above-mentioned preparation step of the precursor.

[0148] In this preparation step, the temperature during the contact reaction between the precursor, the tetravalent titanium halide compound, and the internal electron donor compound is preferably 20 to 105° C., more preferably 20 to 100° C., and even more preferably 25 to 90° C. The time during the contact reaction between the precursor, the tetravalent titanium halide compound, and the internal electron donor compound is preferably 1 to 240 minutes, more preferably 1 to 180 minutes, and even more preferably 30 to 180 minutes.

[0149] The contact and reaction of the magnesium compound, tetravalent titanium halide compound and internal electron donor compound in the precursor preparation step and this preparation step may be carried out in the presence of another electron donor compound as a third component. Examples of the other electron donor compound include organic compounds containing oxygen or nitrogen, such as one or more selected from alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, polysiloxanes, etc.

[0150] Polysiloxane is a polymer with a siloxane bond (-Si-O- bond) in the main chain, and is also known as silicone oil. Its viscosity at 25°C is 0.02 to 100 cm 2 / s (2 to 10,000 centistokes), more preferably 0.03 to 5 cm 2 / s (3 to 500 centistokes) and is liquid or viscous at room temperature.

[0151] Examples of chain polysiloxanes include disiloxanes such as hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, hexaphenyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-dichlorotetramethyldisiloxane, 1,3-dibromotetramethyldisiloxane, chloromethylpentamethyldisiloxane, and 1,3-bis(chloromethyl)tetramethyldisiloxane. Examples of polysiloxanes other than disiloxanes include dimethylpolysiloxane and methylphenylpolysiloxane. Examples of hydrogenated polysiloxanes include methylhydrogenpolysiloxanes with a hydrogenation rate of 10 to 80%, examples of cyclic polysiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, and 2,4,6,8-tetramethylcyclotetrasiloxane, and examples of modified polysiloxanes include higher fatty acid group-substituted dimethylsiloxanes, epoxy group-substituted dimethylsiloxanes, and polyoxyalkylene group-substituted dimethylsiloxanes. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferred, and decamethylcyclopentasiloxane is particularly preferred.

[0152] The treatment of contacting and reacting the magnesium compound, tetravalent titanium halide compound, internal electron donor compound (and optionally polysiloxane), etc. in the precursor preparation step and this preparation step is preferably carried out in the presence of an inert organic solvent.

[0153] The inert organic solvent is preferably a liquid at room temperature (20°C) and has a boiling point of 50 to 150°C, and more preferably an aromatic hydrocarbon compound or a saturated hydrocarbon compound that is a liquid at room temperature and has a boiling point of 50 to 150°C.

[0154] Specific examples of the inert organic solvent include one or more selected from linear aliphatic hydrocarbon compounds such as hexane, heptane, and decane; branched aliphatic hydrocarbon compounds such as methylheptane; alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatic hydrocarbon compounds such as toluene, xylene, and ethylbenzene. Among the above inert organic solvents, aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C are preferred because they can improve the activity of the resulting solid catalyst component and the stereoregularity of the resulting polymer.

[0155] After the reaction in the precursor preparation step or the main preparation step is completed, the obtained reaction product is preferably left to stand, and the supernatant liquid is removed as appropriate to form a wet (slurry) state, or the reaction product is further dried by hot air drying or vacuuming with a vacuum pump, and then washed.

[0156] The above-mentioned cleaning treatment is usually carried out using a cleaning solution.

[0157] Examples of the cleaning liquid include the same inert organic solvents as those described above, and preferably one or more selected from linear aliphatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C, such as hexane, heptane, and decane; cyclic aliphatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C, such as methylcyclohexane and ethylcyclohexane; and aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150°C, such as toluene, xylene, ethylbenzene, and orthodichlorobenzene.

[0158] By using the above-mentioned washing liquid, by-products and impurities can be easily dissolved and removed from the reaction mixture.

[0159] The above-mentioned washing treatment is preferably carried out at a temperature not higher than the boiling point of the washing solution used, and is preferably carried out at a temperature not higher than 90°C.

[0160] The washing treatment is preferably carried out by adding a desired amount of washing liquid to the reaction product, stirring the mixture, and then removing the liquid phase by filtration or decantation.

[0161] After the above components are contacted and reacted, impurities such as unreacted raw material components and reaction by-products (alkoxytitanium halides, titanium tetrachloride-carboxylic acid complexes, etc.) remaining in the reaction product can be removed by washing.

[0162] The contact reaction product of the above components is usually in the form of a suspension, and the suspension product can be left to stand and the supernatant liquid removed to give a wet (slurry) state, and the target solid catalyst component can be obtained by further drying using hot air drying or vacuuming using a vacuum pump.

[0163] Details of the solid catalyst component for olefin polymerization obtained by the production method of the present invention are as described above in the description of the solid catalyst component for olefin polymerization according to the present invention.

[0164] According to the present invention, there can be provided a method for producing a solid catalyst component for olefin polymerization, which can produce, under high activity, polymer particles having a reduced content of fine powder and reduced surface stickiness when subjected to the polymerization of olefins.

[0165] Next, the catalyst for olefin polymerization according to the present invention will be described.

[0166] The catalyst for olefin polymerization according to the present invention comprises: (A) the solid catalyst component for olefin polymerization according to the present invention; (B) an organoaluminum compound; The present invention is characterized in that it comprises:

[0167] (A) Details of the solid catalyst component for olefin polymerization according to the present invention are as described above.

[0168] (B) The organoaluminum compound may be one or more selected from triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, diethylaluminum hydride, ethoxydichloroaluminum, diisopropoxyaluminum, isopropoxychloroaluminum, triethoxyaluminum, triisopropoxyaluminum, etc., and more preferably one or more selected from ethoxydichloroaluminum, diisopropoxyaluminum, isopropoxychloroaluminum, triethoxyaluminum, triisopropoxyaluminum, etc.

[0169] The solid catalyst for olefin polymerization according to the present invention may further contain (C) an external electron donor compound.

[0170] The (C) external electron donor compound includes compounds represented by 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, or an aralkyl group, and R 3 When there are multiple R, they may be the same or different. 3 is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, a vinyl group, an allyl group, or an aralkyl group, and R 3 When a plurality of groups are present, they may be the same or different, and q is an integer of 0≦q≦3.) and the following general formula (III) (R 4 R 5 N)s SiR 6 4-s (III) (In the formula, R 4 and R 5 are 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, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group, and may be the same or different from each other; R 4 and R 5 may be bonded to each other to form a ring. 6 is 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, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group, and R 6 If there are multiple R 6 may be the same or different, and s is an integer of 1 to 3.

[0171] The organosilicon compound represented by the general formula (II) above can include one or more compounds selected from phenylalkoxysilanes, alkylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes, cycloalkylalkylalkoxysilanes, alkoxysilanes, and the like.

[0172] Specific examples of the organosilicon compound represented by the general formula (IV) include di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, and cyclohexylethyldiethoxysilane. Preferably, the silane is at least one selected from the group consisting of cyclohexylcyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane.

[0173] The organosilicon compound represented by the general formula (III) is preferably at least one selected from the group consisting of t-butylmethylbis(ethylamino)silane, bis(ethylamino)dicyclohexylsilane, dicyclopentylbis(ethylamino)silane, bis(perhydroisoquinolino)dimethoxysilane, and diethylaminotriethoxysilane.

[0174] Furthermore, the external electron donor compound (C) can be an ether compound having two or more ether groups. As the ether compound, for example, a 1,3-diether having a substituent at the 2-position is preferable. Examples of the 1,3-diether having a substituent at the 2-position include those represented by the following general formula (IV); R 7 -O-CH2CR 8 R 9 CH2-OR 10 (IV) (In the formula, R 8 and R 9R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group or a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic hydrocarbon group or a halogen-substituted aromatic hydrocarbon group having 6 to 12 carbon atoms, an aromatic hydrocarbon group having 7 to 12 carbon atoms and having a substituent, an alkylamino group having 1 to 12 carbon atoms, or a dialkylamino group having 2 to 12 carbon atoms, and may be the same or different and may be bonded to each other to form a ring. 7 and R 10 represents 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 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a halogen-substituted aromatic hydrocarbon group, or an aromatic hydrocarbon group having 7 to 12 carbon atoms and having a substituent, and may be the same or different.

[0175] Specific examples include 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene. Among these, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene are preferably used, and at least one or two or more of these compounds can be used.

[0176] In the catalyst for olefin polymerization according to the present invention, the content ratios of (A) the solid catalyst component for olefin polymerization according to the present invention, (B) the organoaluminum compound, and (C) the external electron donor compound can be arbitrarily selected within a range in which the effects of the present invention can be obtained, and are not particularly limited.

[0177] The catalyst for olefin polymerization according to the present invention preferably contains 1 to 2000 moles, more preferably 50 to 1000 moles, of (B) an organoaluminum compound per mole of titanium atoms constituting (A) the solid catalyst component for olefin polymerization according to the present invention.

[0178] The catalyst for olefin polymerization according to the present invention preferably contains 1 to 200 moles, more preferably 2 to 150 moles, and even more preferably 5 to 100 moles of (C) an external electron donor compound per mole of titanium atoms constituting (A) the solid catalyst component for olefin polymerization according to the present invention.

[0179] The catalyst for olefin polymerization according to the present invention can be produced by mutually contacting (A) the solid catalyst component for olefin polymerization according to the present invention, (B) an organoaluminum compound, and, if necessary, (C) an external electron donor compound.

[0180] In the method for producing the olefin polymerization catalyst according to the present invention, the above components may be contacted in any order, but the following contact order can be exemplified. (i) (A) the solid catalyst component for olefin polymerization according to the present invention → (C) an external electron donor compound → (B) an organoaluminum compound (ii) (B) organoaluminum compound → (C) external electron donor compound → (A) solid catalyst component for olefin polymerization according to the present invention (iii) (C) external electron donor compound → (A) the solid catalyst component for olefin polymerization according to the present invention → (B) organoaluminum compound (iv) (C) external electron donor compound → (B) organoaluminum compound → (A) the solid catalyst component for olefin polymerization according to the present invention

[0181] Of the above examples (i) to (iv), example (ii) is preferred.

[0182] In the above contact examples (i) to (iv), "→" indicates the order of contacting. For example, "(A) the solid catalyst component for olefin polymerization according to the present invention → (B) the organoaluminum compound → (γ) the external electron donor compound" means that (A) the solid catalyst component for olefin polymerization according to the present invention is contacted with (B) the organoaluminum compound, and then (C) the external electron donor compound is added and contacted.

[0183] In the method for producing the catalyst for olefin polymerization according to the present invention, the solid catalyst component for olefin polymerization, the organoaluminum compound, and the external electron donor compound (C) added as needed may be contacted in the absence of olefins or in the presence of olefins (in the polymerization system).

[0184] The contact of the (A) solid catalyst component for olefin polymerization according to the present invention with the (B) organoaluminum compound and the (C) external electron donor compound added as needed is preferably carried out in an inert gas atmosphere such as argon or nitrogen, or in a monomer atmosphere such as propylene, in order to prevent deterioration of the solid catalyst component for olefin polymerization and the catalyst for olefin polymerization after production.

[0185] In addition, in consideration of ease of operation, it is also preferable to carry out the reaction in the presence of a dispersion medium such as an inert solvent. Examples of the inert solvent include aliphatic hydrocarbon compounds such as hexane, heptane, and cyclohexane, and aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene. Aliphatic hydrocarbons are more preferred, and hexane, heptane, and cyclohexane are particularly preferred.

[0186] The contact temperature when the above components are brought into contact is preferably −10° C. to 100° C., more preferably 0° C. to 90° C., and even more preferably 20° C. to 80° C. The contact time is preferably 1 minute to 10 hours, more preferably 10 minutes to 5 hours, and even more preferably 30 minutes to 2 hours.

[0187] By setting the contact temperature and contact time within the above ranges, it becomes easier to improve the polymerization activity of the olefin polymerization catalyst and the stereoregularity of the resulting polymer, and as a result, it becomes easier to improve the mechanical properties, processability, and productivity of the resulting olefin polymer.

[0188] According to the present invention, it is possible to provide a catalyst for olefin polymerization which, when used in the polymerization of olefins, can produce polymer particles with a reduced content of fine powder and reduced surface stickiness under high activity.

[0189] Next, the method for producing the olefin polymer particles according to the present invention will be described.

[0190] The method for producing olefin polymer particles according to the present invention is characterized in that olefins are polymerized using the olefin polymerization catalyst according to the present invention.

[0191] In the method for producing olefin polymer particles according to the present invention, the polymerization of olefins may be homopolymerization or copolymerization.

[0192] In the method for producing olefin polymer particles according to the present invention, the olefin to be polymerized is preferably an α-olefin having 2 to 8 carbon atoms, and when the olefin is polymerized as a homopolymer, ethylene or propylene is preferred, and when the olefin is polymerized as a copolymer, propylene and a monomer of another α-olefin having 2 to 8 carbon atoms (excluding an α-olefin having 3 carbon atoms) are more preferred. The other α-olefin to be copolymerized with propylene is preferably one or more selected from ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., more preferably ethylene or 1-butene, and even more preferably ethylene.

[0193] The amount of the other α-olefins to be copolymerized with propylene is preferably an amount that is contained in the resulting copolymer in an amount of 0.1 to 30 mol %.

[0194] In the method for producing olefin polymer particles according to the present invention, for example, when copolymerizing propylene with other α-olefins, typical methods include random copolymerization in which propylene and a small amount of ethylene are polymerized in one stage as comonomers, and so-called propylene-ethylene block copolymerization in which propylene is homopolymerized in the first stage (first polymerization vessel) and then copolymerized with propylene and other α-olefins such as ethylene in the second stage (second polymerization vessel) or multiple stages (multistage polymerization vessels), and block copolymerization of propylene with other α-olefins is preferred.

[0195] A block copolymer obtained by block copolymerization is a polymer containing segments in which the composition of two or more monomers changes continuously, and is a polymer in which two or more types of polymer chains (segments) with different primary structures, such as monomer type, comonomer type, comonomer composition, comonomer content, comonomer sequence, and stereoregularity, are connected in a single molecular chain.

[0196] In the method for producing olefin polymer particles of the present invention, the polymerization of olefins can be carried out in the presence or absence of an organic solvent. The olefins to be polymerized may be used in either a gaseous or liquid state.

[0197] The polymerization of olefins is carried out, for example, in a reactor such as an autoclave, by introducing olefins into the reactor in the presence of the olefin polymerization catalyst according to the present invention under heated and pressurized conditions.

[0198] In the method for producing olefin polymer particles according to the present invention, the polymerization temperature is usually 200° C. or lower, preferably 100° C. or lower, and from the viewpoint of improving activity and stereoregularity, more preferably 60 to 100° C., even more preferably 70 to 90° C., and still more preferably 75 to 80° C. In the method for producing olefin polymer particles according to the present invention, the polymerization pressure is preferably 10 MPa or lower, more preferably 6 MPa or lower, and even more preferably 5 MPa or lower.

[0199] Details of the olefin polymer particles obtained by the production method according to the present invention are as described below in the description of the olefin polymer particles according to the present invention.

[0200] According to the present invention, there can be provided a method for producing olefin polymer particles, which can produce polymer particles with a reduced content of fine powder and reduced surface stickiness under high activity.

[0201] Next, the olefin polymer particles according to the present invention will be described.

[0202] The olefin polymer particles according to the present invention have a cross-sectional pore area ratio (pore area ratio in the cross section of the olefin polymer particle) of 10 to 50%, The cross-sectional pore area ratio (M'X) of the region 50% or more in the radial direction from the particle center s ) to the cross-sectional pore area ratio (M'X i ) ratio M'X i / MX s is 0.50 to 2.00 It is characterized by the following.

[0203] The cross-sectional pore area ratio of the olefin polymer particles according to the present invention is 10 to 50%, preferably 15 to 50%, and more preferably 18 to 50%.

[0204] The cross-sectional pore area ratio (M'X) of the region of 50% or more in the radial direction from the particle center of the olefin polymer particle according to the present invention is s ) to the cross-sectional pore area ratio (M'X i ) ratio M'X i / M'X s is 0.50 to 2.00, preferably 0.80 to 2.00, more preferably 1.00 to 2.00, and even more preferably 1.00 to 1.50.

[0205] The ratio M'X of the cross-sectional pore area ratio and the average pore area ratio of the olefin polymer particles according to the present invention i / M'Xs The method for measuring the ratio MX of the cross-sectional pore area ratio and the average pore area ratio of the solid catalyst component for olefin polymerization according to the present invention is as follows: i / MX s The measurement method is the same as that of In the olefin polymer particles according to the present invention, 500 polymer particles (500 particles) are cut and processed by the method described above, and the arithmetic mean values ​​of the cross-sectional pore area ratio, the cross-sectional pore area ratio of a region at least 50% in the radial direction from the particle center, and the cross-sectional pore area ratio of a region less than 50% in the radial direction, which are determined by the same method as described above, are respectively referred to as the cross-sectional pore area ratio, the cross-sectional pore area ratio of a region at least 50% in the radial direction from the particle center (M'X s ) and the cross-sectional pore area ratio of the region less than 50% in the radial direction (M'X i ) shall be as follows.

[0206] The olefin polymer particles according to the present invention may be either a homopolymer or a copolymer. Details of the olefins constituting the copolymer and the polymerization conditions for the olefins are as described in the description of the olefin polymer particles according to the present invention.

[0207] The olefin polymer particles according to the present invention preferably have an average particle size of 100 to 5000 μm, more preferably 250 to 4000 μm, and even more preferably 300 to 3000 μm.

[0208] In the present application, the average particle size of the olefin polymer particles is the average particle size D measured using a laser light scattering diffraction particle size analyzer. 50 (The particle size of 50% of the cumulative particle size in the volume cumulative particle size distribution).

[0209] The olefin polymer particles according to the present invention preferably contain 0.5% by mass or less of fine polymer powder having a particle size of 45 μm or less, more preferably 0.3% by mass or less, and even more preferably 0 to 0.1% by mass.

[0210] In the olefin polymer particles according to the present invention, the content of fine powder means the content (mass%) of polymers having a particle size of less than 45 μm when the volume-based cumulative particle size distribution of the polymer is automatically measured using a digital image analysis particle size distribution measuring device (Camsizer, manufactured by Horiba, Ltd.).

[0211] The olefin polymer particles according to the present invention preferably have a flowability measured by the following method of 5 to 15 g / sec, more preferably 5 to 10 g / sec, and even more preferably 5 to 9 g / sec. <Flowability of polymer> As shown in Figure 10, a funnel F (top diameter: 91 mm, damper position diameter: 8 mm, inclination angle: 20°, height to damper position: 114 mm) with a damper D installed at the outlet position was set at the top, and a container-shaped receiver C (inner diameter: 40 mm, height: 81 mm) was placed below the damper D with a gap of 38 mm. An apparatus was used, in which 50 g of polymer was first charged into the upper funnel F, and then, at room temperature (20°C), the damper D was opened to allow the polymer to fall into the receiver C, and the time it took for all the polymer to fall was measured. The falling time T of 50 g of polymer measured by the above operation 1 From the time (seconds), the amount of polymer falling per second (g / second) was calculated using the following formula, and this was used as an evaluation index for polymer fluidity. Flowability of polymer particles (amount of polymer falling per second (g / sec)) = 50 ÷ T 1

[0212] When the olefin polymer particles according to the present invention have flowability within the above range, the surface is prevented from becoming sticky, and excellent handling, processability and transportability can be easily exhibited.

[0213] The olefin polymer particles according to the present invention can be suitably produced by the above-mentioned method for producing olefin polymer particles according to the present invention.

[0214] According to the present invention, it is possible to provide olefin polymer particles in which the content of fine powder is reduced and the stickiness of the surface is reduced. [Example]

[0215] Next, the present invention will be explained in more detail by way of examples, but these are merely illustrative and do not limit the present invention.

[0216] The cross-sectional pore area ratios shown below are the cross-sectional pore area ratios of the region 50% or more in the radial direction from the particle center (MX s ) to the cross-sectional pore area ratio (MX i ) is the ratio of MX i / MX s , cross-sectional pore area ratio of the region of 50% or more in the radial direction (M'X s ) to the cross-sectional pore area ratio (M'X i ) is the ratio of M'X i / M'X s and the cross-sectional pore area ratio (M''X s ) to the cross-sectional pore area ratio (M''X i ) is the ratio of M''X i / M''X s was determined by forming a thermally conductive coating on the particle surface using the following method, then processing the cross section of the particle with CCP, and then observing the cross section with an SEM device and measuring it with EDS.

[0217] <Formation of thermally conductive coating> An ion sputter (JEOL Ltd., JFC-1600) equipped with a gold target for deposition and a rotating stage is placed in a glove box for deposition work that has been thoroughly purged with nitrogen. The particles to be measured, a spatula, an aluminum shallow container, a silicon wafer (5 mm long x 10 mm wide x 0.2 mm thick) with conductive double-sided tape attached in advance, and a sealed CCP transfer vessel (JEOL Ltd., model number IB-19520 for CCP) are then placed in the glove box, and the inside of the glove box is thoroughly purged with nitrogen.

[0218] An aluminum shallow-bottom container containing about 500 mg of measurement particles was set in an ion sputter, and gold evaporation was carried out while rotating the stage at a speed of 30 rpm under the conditions of a final vacuum of 15 Pa or less and an applied voltage of 30 mA. Next, the aluminum shallow-bottom container containing the gold-evaporated measurement particles was once taken out from the evaporator, the solid catalyst components in the shallow-bottom container were mixed with a spatula, and then it was set again in the vacuum evaporator, and gold evaporation was carried out for 5 minutes while rotating the stage at a speed of 30 rpm under the conditions of a final vacuum of 15 Pa or less and an applied voltage of 30 mA. A series of such operations was repeated 3 times to form a gold evaporation film on the entire surface of the measurement particles.

[0219] <CCP cross-section processing> Next, in a glove box for evaporation work that was sufficiently purged with nitrogen, gold-evaporated measurement particles were scattered on the surface of the conductive double-sided tape attached to the silicon wafer in an amount such that the particles did not overlap each other. After storing the silicon wafer in a transfer vessel for a sealed CCP, the transfer vessel taken out from the glove box was fixed to a CCP cross-section processing apparatus (manufactured by JEOL Ltd., model number IB-19520 CCP). Next, while maintaining the following vacuum of 10 -3 While maintaining the CCP stage temperature at -110°C or lower while maintaining the following, the argon ion beam was turned on for 10 seconds and then turned off for 10 seconds, and the operation was repeated. In a so-called intermittent measurement method, cross-section processing of the solid catalyst component was carried out at an acceleration voltage of 3.0 kV for 6 hours.

[0220] <Cross-section observation by SEM apparatus and EDS measurement> JSM-F100 manufactured by JEOL Ltd. was used for the SEM. The cross-section processed sample was set together with the transfer vessel removed from the CCP cross-section processing apparatus, and observation was carried out by the reflected electron image of the cross-section processing part as illustrated in FIG. 1 at an acceleration voltage of 5 kV

[0221] <The The SEM image shown in FIG. 1 was used with Adobe Photoshop software. After cutting out the contour part of the particle image as shown in FIG. 2, a binary image was created. Then, the same procedure was carried out for 500 particles whose cross sections had been processed for measurement, and the cross-sectional pore area ratios (%) of the precursor (B), the solid catalyst component (C), and the polymer, and the M''X of the precursor (B) were calculated by the above-mentioned calculation method. i / M''X s and the ratio MX of the average pore area ratio of the solid catalyst component (C) i / MX s and the ratio of the average pore area ratio of the polymer M'X i / M'X s and asks for.

[0222] (Production Example 1) <Synthesis of Complex (A) of Titanium Tetrachloride with Internal Electron Donor Compound> 200 mL of n-heptane and 0.5 mol of di-n-butyl phthalate were added to a 1,000 mL three-neck flask equipped with a dropping funnel and the atmosphere had been replaced with nitrogen. Next, while maintaining the temperature inside the flask at 40°C, 0.5 mol of titanium tetrachloride was added to the dropping funnel, and then the titanium tetrachloride was added dropwise to the flask.

[0223] After the dropwise addition of titanium tetrachloride was completed, the three-neck flask was kept at 40°C and reacted for 2 hours, after which it was washed with n-heptane until all the free titanium components were gone. Finally, it was dried using a vacuum pump until all the n-heptane was gone, yielding a yellow solid powder of titanium tetrachloride and di-n-butyl phthalate complex (A).

[0224] The titanium content of a sample of the obtained yellow solid powdery complex (A) was measured in accordance with the method of Japanese Industrial Standard "JIS M 8301." Assuming that all titanium atoms in the sample were titanium tetrachloride, the titanium tetrachloride content (mol) and the di-n-butyl phthalate content (mol) were calculated, and the molar ratio expressed as di-n-butyl phthalate / titanium atoms was found to be 1.09.

[0225] <Preparation of precursor (B)> Into a nitrogen-substituted 100 mL stainless steel portable reactor (Taiatsu Glass Industry Co., Ltd., TVS-1 Type), 30 g of diethoxymagnesium, 5.0 g of the obtained yellow solid powder complex (A), and 50 mL of toluene were added.

[0226] Here, the diethoxy magnesium used in Production Example 1 has a bulk density of 0.32 g / mL and an average particle size D 50 The particle size distribution index (SPAN) measured by the following method is 0.8. The physical properties of diethoxy magnesium are shown in Table 1.

[0227] Next, the stainless steel portable reactor was pressurized to a gauge pressure of 0.9 MPa using nitrogen and maintained at 25°C for 2 hours. Thereafter, the nitrogen pressure in the stainless steel portable reactor was returned to normal pressure (less than 0.01 MPa), and finally, the particles were washed with n-heptane and dried to obtain precursor (B). At this time, when 500 particles were randomly selected from precursor (B), the cross-sectional pore area ratio was 38%, and the cross-sectional pore area ratio (M''X) of the region of 50% or more in the radial direction was 100%. s ) to the cross-sectional pore area ratio (M''X i ) ratio M''X i / M''X s The ratio was 1.01. The physical properties of the precursor (B) are shown in Table 1.

[0228] <Particle size distribution index (SPAN)> The particle size distribution index (SPAN) of the diethoxy magnesium used in each manufacturing example is the average particle diameter D 50 (50% particle size in the volumetric particle size distribution) and the average particle size D 50 The particle size was calculated using the following formula using the 90% particle size and the 10% particle size of the volume-based integrated particle size measured at the same time when the measurement was performed. Particle size distribution index (SPAN) = (particle size of 90% of the volume-based cumulative particle size - particle size of 10% of the volume-based cumulative particle size) / particle size of 50% of the volume-based cumulative particle size (average particle size D 50 )

[0229] Example 1 <Preparation of solid catalyst component (C)> In a 500 mL round-bottom flask equipped with a stirrer and a reflux condenser and purged with nitrogen gas, 20 g of the precursor (B) obtained in Production Example 1, 160 mL of toluene, and 4.8 mL of di-n-butyl phthalate were placed to form a suspension, which was maintained at −5° C.

[0230] Meanwhile, 20 mL of titanium tetrachloride and 40 mL of toluene were placed in a 500 mL round-bottom flask equipped with a stirrer and purged with nitrogen gas. The resulting mixed solution was kept at -4°C, and the above suspension was added to this mixed solution to form a mixed suspension. Thereafter, this mixed suspension was heated and reacted at 105°C for 2 hours with stirring to obtain a solid product.

[0231] After the reaction was completed, the obtained solid product was washed three times with 200 mL of toluene at 90°C, and then 20 mL of titanium tetrachloride and 80 mL of toluene were added. The mixture was heated to 110°C and reacted for 1 hour with stirring. After removing the supernatant by decantation, the mixture was washed ten times with 120 mL of n-heptane at 40°C and finally dried to obtain the desired solid catalyst component (C). The cross-sectional pore area ratio of the particles of the solid catalyst component (C) at this time was 36%, and the cross-sectional pore area ratio (MX s ) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s The ratio was 1.01. The physical properties of the solid catalyst component (C) are shown in Table 2.

[0232] <Formation of olefin polymerization catalyst and propylene homopolymerization> A catalyst for olefin polymerization was prepared by charging 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane, and 0.0033 mmol, calculated as titanium atom, of the solid catalyst component obtained in the step <Preparation of solid catalyst component (C)> into a 2.0-liter autoclave equipped with a stirrer and whose interior was completely purged with nitrogen gas.

[0233] Thereafter, 1.5 liters of hydrogen gas and 1.0 liter of liquefied propylene were charged, and a polymerization reaction was carried out at 70°C for 1 hour to obtain a propylene polymer (polymer). The polymerization activity at this time was calculated using the following formula, and the average particle size D of the obtained propylene polymer was calculated using the following formula. 50 The content of fine powder of 45 μm or less was measured as an index of the fine powder content by the following method. The results are shown in Table 2.

[0234] <Polymerization activity> Polymerization activity (g-pp / g-catalyst) = mass of polymer (g) / mass of solid catalyst component (g)

[0235] <Average particle size D 50 , Fine powder content of 45 μm or less> Using a digital image analysis particle size distribution analyzer (Camsizer, manufactured by Horiba, Ltd.), the volume-based cumulative particle size distribution of the polymer was automatically measured under the following measurement conditions. The amount of fine powder (mass%) with a particle size of less than 45 μm and the particle size of 50% of the volume-based cumulative particle size (average particle size D 50 ) was measured. (Measurement conditions) Funnel position: 6mm Camera coverage: 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 ratio: 50% (1:2) Particle size definition: The minimum Martin diameter measured n times for each particle SPHT (sphericity) fitting: 1 Upper limit of class: Logarithmic scale, 50 points selected in the range of 32 to 4000 μm

[0236] <Ethylene-propylene copolymer> Into an autoclave with a capacity of 2.0 liters equipped with a stirrer and completely replaced with nitrogen gas, 2.4 mmol of triethylaluminum, 0.24 mmol of cyclohexylmethyldimethoxysilane, and 6 mg of the solid catalyst component obtained above were charged to prepare an ethylene-propylene copolymerization catalyst. Into an autoclave with a stirrer containing the ethylene-propylene copolymerization catalyst prepared above, 15 mol (1.2 liters) of liquefied propylene and 0.20 MPa (partial pressure) of hydrogen gas were charged. After pre-polymerization was carried out at 20 °C for 5 minutes, the temperature was raised, and after the first-stage propylene homopolymerization reaction (single-stage polymerization) was carried out at 70 °C for 45 minutes, the pressure was returned to normal pressure. Then, the inside of the autoclave (inside the reactor) was purged with nitrogen and then the autoclave was weighed. After subtracting the tare weight of the autoclave, the polymerization activity (g-PP / g-catalyst) of the single stage (first stage) was calculated by the same method as described above. A part of the produced polymer was separated for evaluation of the polymerization performance and polymer physical properties (pore volume). Next, ethylene / propylene were charged into the autoclave (inside the reactor) so that the molar ratio was 1.0 / 1.0 respectively. After the temperature was raised to 70 °C, ethylene / propylene / hydrogen were introduced while the gas supply rate (liter / min) per minute was in the ratio of 2 / 2 / 0.086, and the reaction was carried out under the conditions of 1.2 MPa, 70 °C, and 60 minutes to obtain an ethylene-propylene copolymer. Regarding the produced ethylene-propylene copolymer particles, the propylene-based block copolymerization activity (ICP (impact copolymer) polymerization activity), the EPR (ethylene-propylene rubber component) content (wt%) in the obtained propylene-based block copolymer, the fluidity of the copolymer particles, and the EPR (ethylene-propylene rubber component) dispersion state inside the polymer particles were measured by the following methods respectively. The results are shown in Table 3.

[0237] <ICP polymerization activity> The propylene-based block copolymerization activity per 1 g of the solid catalyst component was determined by the following formula. Propylene-based block copolymerization activity (g-ICP / g-catalyst) = (I(g) - F(g) + J(g)) / [{mass (g) of the solid catalyst component in the catalyst for olefin polymerization × ((G(g) - F(g) - J(g))} / (G(g) - F(g)))] Here, I is the mass (g) of the autoclave after the copolymerization reaction is completed, F is the mass (g) of the autoclave, G is the mass (g) of the autoclave after the propylene homopolymerization is completed and the unreacted monomer is removed, and J is the amount (g) of polymer withdrawn after the homopolymerization.

[0238] <EPR content in copolymer (amount of xylene solubles in copolymer)> A flask equipped with a stirrer was charged with 5.0 g of copolymer (ICP propylene polymer) and 250 ml of p-xylene. The external temperature was raised above the boiling point of xylene (approximately 150°C), and the temperature of the p-xylene inside the flask was maintained below the boiling point (137-138°C) while dissolving the polymer over 2 hours. The liquid temperature was then cooled to 23°C over 1 hour, and the insoluble and soluble components were separated by filtration. The solution of the soluble components was collected and dried under reduced pressure to remove the p-xylene. The weight of the resulting residue was determined, and the relative proportion (mass%) to the produced polymer (propylene-based block copolymer) was calculated to represent the EPR (ethylene-propylene rubber component) content.

[0239] <Flowability of copolymer particles> The flowability of the produced polymer was measured by the following method. As shown in Figure 10, a funnel F (upper opening diameter: 91 mm, damper opening diameter: 8 mm, inclination angle: 20°, height to damper position: 114 mm) with a damper D installed at the outlet position was set at the top, and a container-shaped receiver C (inner diameter: 40 mm, height: 81 mm) was placed below the damper D with a gap of 38 mm. An apparatus was used, in which 50 g of polymer was first charged into the upper funnel F, and then, at room temperature (20°C), the damper D was opened to allow the polymer to fall into the receiver C, and the time it took for all the polymer to fall was measured. The falling time T of 50 g of polymer measured by the above operation 1From the time (seconds), the amount of polymer falling per second (g / sec) was calculated using the following formula, and used as an evaluation index for polymer fluidity. Polymer fluidity (amount of polymer falling per second (g / sec)) = 50 ÷ T 1

[0240] <Internal observation of copolymer particles> The interior of the produced copolymer particles was observed and the degree of pore dispersion was determined by the following method. Two hundred randomly selected copolymer particles were stained for EPR components with ruthenium tetroxide at a concentration of 5 for 5 minutes using a vacuum electron staining apparatus (VSC1R1H) manufactured by Filgen. Using Epocure 2 manufactured by Buhler, a mixture of 80% by weight of resin and 20% by weight of hardener was prepared. The dyed copolymer particles and the prepared Epocure 2 were mixed in a 1-inch transparent cup and left at room temperature until hardened. The 1-inch cup containing the cured product obtained by mixing and curing as described above was cut using a Buhler isometric cutter so that it could be polished, and the cut pieces were carefully wet-polished with water using a JEOL Ltd. precision surface polishing machine, HandyLap (HLA-2), with abrasive paper of #600 (JIS standard) to #5,000 (JIS standard). Finally, three full-load barrels were placed on a Buehler Automet 250, Mastertex was attached to the polishing buff, tap water was used as the extender, and the rotation speed was set to 60 rpm for the head and 150 rpm for the base, in the same direction, for 90 seconds for the final finish, and the moisture was blown off with air. The cross section of the obtained copolymer particles was observed with ECLIPSE LV100NDA manufactured by Nikon Corporation. In the obtained micrograph, the black areas were EPR-filled areas stained with ruthenium tetroxide (pores filled with ethylene-propylene rubber), and the white areas were PP areas (propylene homopolymer areas). In this example, it was confirmed that almost all of the pores observed in the cross section of the copolymer particle were filled with EPR. The ratio MX of the cross-sectional pore area ratio and the average pore area ratio of the above-mentioned solid catalyst component for olefin polymerization i / MX s In the measurement method (image analysis method) of (1), the cross-sectional image of the copolymer particle was changed to a two-tone particle cross-sectional image (as shown in Figure 4), and the PP portion was used instead of the texture portion (flat portion), and the EPR-filled portion was used instead of the pore portion (recessed portion). In the copolymer particle cross-section, the cross-sectional pore area ratio (M'X s ) and the cross-sectional pore area ratio of the region less than 50% in the radial direction (M'X i ) were calculated, the cross-sectional pore area ratio (M'X s ) to the cross-sectional pore area ratio (M'X i ) ratio M'X i / M'X s The ratio was 1.02. The results are shown in Table 3.

[0241] (Production Example 2) The synthesis of complex (A) and the preparation of precursor (B) were carried out in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, the amount of titanium tetrachloride and di-n-butyl phthalate complex (A) added was changed from 5.0 g to 1.0 g.

[0242] Example 2 Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 2, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0243] (Production Example 3) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, the amount of titanium tetrachloride and di-n-butyl phthalate complex (A) added was changed from 5.0 g to 7.0 g.

[0244] Example 3 Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 3, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0245] (Production Example 4) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, 30 g of diethoxymagnesium having a bulk density of 0.20 g / mL, an average particle size of 15 μm, and a particle size distribution index (SPAN) of 1.2 was used.

[0246] Example 4 Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 4, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0247] (Production Example 5) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, 30 g of diethoxymagnesium having a bulk density of 0.35 g / mL, an average particle size of 102 μm, and a particle size distribution index (SPAN) of 1.5 was used.

[0248] Example 5 Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 5, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0249] (Production Example 6) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, 30 g of diethoxymagnesium having a bulk density of 0.33 g / mL, an average particle size of 74 μm, and a particle size distribution index (SPAN) of 1.2 was used.

[0250] Example 6 Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 6, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0251] (Production Example 7) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, 30 g of diethoxymagnesium having a bulk density of 0.24 g / mL, an average particle size of 19 μm, and a particle size distribution index (SPAN) of 0.9 was used.

[0252] Example 7 Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 7, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0253] (Production Example 8) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, 30 g of diethoxymagnesium having a bulk density of 0.20 g / mL, an average particle size of 9.8 μm, and a particle size distribution index (SPAN) of 1.2 was used.

[0254] Example 8 Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 8, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0255] (Production Example 9) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, 30 g of diethoxymagnesium having a bulk density of 0.37 g / mL, an average particle size of 112 μm, and a particle size distribution index (SPAN) of 1.6 was used.

[0256] (Comparative Example 1) Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 9, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0257] (Production Example 10) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, the inside of the stainless steel portable reactor was pressurized to a gauge pressure of 0.1 MPa and maintained at 90°C for 2 hours, instead of being pressurized to a gauge pressure of 0.9 MPa and maintained at 25°C for 2 hours.

[0258] Example 9 Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 10, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0259] (Production Example 11) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, the inside of the stainless steel portable reactor was pressurized to a gauge pressure of 0.9 MPa and maintained at 90°C for 24 hours, instead of being pressurized to a gauge pressure of 0.9 MPa and maintained at 25°C for 2 hours.

[0260] Example 10 Except for preparing the solid catalyst component (C) using the precursor (B) obtained in Production Example 11, the preparation of the solid catalyst component (C), the formation of the polymerization catalyst, and the polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0261] (Manufacturing Example 12) Complex (A) was synthesized and precursor (B) was obtained in the same manner as in Production Example 1, except that in the <Preparation of precursor (B)> step, 30 g of diethoxymagnesium having a bulk density of 0.20 g / mL, an average particle size of 78 μm, and a particle size distribution index (SPAN) of 1.2 was used.

[0262] (Comparative Example 2) Preparation of the solid catalyst component (C), formation of the polymerization catalyst, and polymerization were carried out in the same manner as in Example 1, except that the solid catalyst component (C) was prepared using the precursor (B) obtained in Production Example 12, and each was evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

[0263] (Comparative Example 3) Using a solid catalyst component corresponding to a comparative example of the present invention, the formation of a polymerization catalyst and polymerization were carried out in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. A photograph of a cross section of the copolymer particle obtained at this time (before the two-tone processing) is shown in FIG. In Figure 11, it was confirmed that the EPR-filled areas (pores filled with ethylene-propylene rubber) stained with ruthenium tetroxide, shown in black, are distributed relatively throughout the particle cross section, extending from the periphery to the center, in contrast to the PP areas (propylene homopolymer areas) shown in white.

[0264] [Table 1]

[0265] [Table 2]

[0266] [Table 3]

[0267] From Tables 2 and 3, in Examples 1 to 10, the solid catalyst components constituting the catalysts for olefin polymerization had a cross-sectional pore area ratio of 10 to 50%, and a cross-sectional pore area ratio (MX s ) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s Since the ratio is 0.50 to 2.00, it is understood that a polymer with a reduced content of fine powder can be produced under high activity. This means that the solid catalyst component has a specific cross-sectional pore area ratio and MX i / MX s It is believed that this is because, by having such a structure, catalyst particles having high strength and not easily broken during polymerization and a low content of fine particles can be formed. In addition, by using the above solid catalyst components, the MX of each solid catalyst component i / MX s M'X corresponding to i / M'X s It is found that it is possible to produce a polymer having the above formula (see Tables 2 and 3), and the resulting copolymer particles have low flowability and can suppress surface stickiness (see Table 3). This is the specific cross-sectional pore area ratio and MX of the solid catalyst component. i / MX s By using a solid catalyst component having the above structure, it is possible to produce copolymer particles with a specific pore distribution, and it is thought that the presence of EPR (ethylene-propylene rubber) exclusively in the peripheral pores of the copolymer microporous skeleton structure formed by PP (propylene homopolymer) suppresses surface adhesion and exudation of the rubber component, thereby suppressing stickiness. Therefore, in Examples 1 to 10, when used in the polymerization of olefins, it is possible to produce polymer particles under high activity that have a reduced content of fine powder and have low flowability and suppressed stickiness on the polymer particle surface.

[0268] On the other hand, from Tables 2 and 3, in Comparative Examples 1 and 2, in the solid catalyst components constituting the catalyst for olefin polymerization, the cross-sectional pore area ratio was outside the range of 10 to 50%, and the cross-sectional pore area ratio (MX s ) to the cross-sectional pore area ratio (MX i ) ratio MX i / MX s Since the value is outside the range of 0.50 to 2.00, when the polymer is subjected to the polymerization of olefins, the polymer particles obtained have a high content of fine powder (Table 2), and the flowability is high, resulting in high stickiness on the surface of the polymer particles (Table 3). [Industrial Applicability]

[0269] According to the present invention, it is possible to provide a solid catalyst component for olefin polymerization which, when subjected to the polymerization of olefins, can suitably produce polymer particles having a reduced content of fine powder and reduced surface stickiness under high activity, and it is also possible to provide a method for producing the solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for producing olefin polymer particles, and olefin polymer particles.

Claims

1. containing magnesium, titanium, halogens and internal electron donor compounds, The cross-sectional pore area ratio is 10 to 50%, The cross-sectional pore area ratio (MX) of the region of 50% or more in the radial direction from the particle center ｓ ) to the cross-sectional pore area ratio (MX ｉ ) ratio MX ｉ / MX ｓ is 0.50 to 2.00 A solid catalyst component for olefin polymerization, characterized in that:

2. A method for producing the solid catalyst component for olefin polymerization according to claim 1, comprising: A method for producing a solid catalyst component for olefin polymerization, comprising contacting a magnesium compound, a tetravalent titanium halide compound, and an internal electron donor compound under pressure to prepare a precursor, and then contacting the precursor with a tetravalent titanium halide compound and an internal electron donor compound.

3. (A) the solid catalyst component for olefin polymerization according to claim 1; (B) an organoaluminum compound; A catalyst for olefin polymerization, comprising:

4. The catalyst for olefin polymerization according to claim 3, further comprising (C) an external electron donor compound.

5. A method for producing olefin polymer particles, which comprises polymerizing olefins using the catalyst for olefin polymerization according to claim 3 or 4.

6. The cross-sectional pore area ratio is 10 to 50%, The cross-sectional pore area ratio (M'X) of the region of 50% or more in the radial direction from the particle center ｓ ) to the cross-sectional pore area ratio (M'X ｉ ) ratio M'X ｉ / M'X ｓ is 0.50 to 2.00 1. Olefin polymer particles comprising:

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