Method for producing magnesium compound particles, method for controlling shape of olefin polymer particles, and olefin polymer particles

Abstract

[Problem] To provide a method for producing particles that contain magnesium atoms and specific metal atoms and have a small average particle diameter, said particles being useful in the production of fine olefin polymer particles having uneven surfaces. [Solution] A magnesium-containing compound liquid is brought into contact with an organometallic compound containing a specific metal atom under specific conditions to produce particles that contain magnesium atoms and specific metal atoms at a specific ratio and that have a specific average particle diameter. The particles obtained by the above-described particle diameter and atomic ratio are useful in the production of fine olefin polymer particles having uneven shapes on the surface.

Description

Technical Field

[0001] The present invention relates to a method for producing magnesium compound particles, a method for controlling the shape of olefin polymer particles, and olefin polymer particles. Background Art

[0002] In recent years, the development of polymer particles has been active and widely used in various applications in the industry. Among them, polymer particles with a spherical particle shape and a narrow particle size distribution are used for applications such as filters, separation membranes, dispersants, powder coatings, resin modifiers, and coating agents due to their good processability, fluidity, and surface properties. The materials of these polymer particles are known to have materials such as acrylic resins, styrene resins, and melamine resins, which are mainly manufactured by emulsion polymerization. On the other hand, polyolefin particles are also known. Polyolefin particles are hydrocarbon materials with high crystallinity, high melting points, and substantially no heteroatoms. Therefore, high chemical stability, specifically water resistance / oil resistance, chemical resistance, and biological safety are effectively utilized. Various new materials and new applications have been proposed and put into practical application.

[0003] For example, polyethylene microparticles, either directly or through surface modification, can be used as column packings for efficient separations of chemical and biological substances, as high-specific-surface-area adsorbents, catalyst supports, etc. Furthermore, they can be used as carriers for the delivery and release of drugs, as dispersants for uniformly dispersing poorly dispersible microparticles, and as safe microparticle materials that provide a pleasant feel to the skin as raw materials for cosmetics.

[0004] In addition, we are actively researching their applications in new functional materials, including components for diaphragms in lithium batteries and lithium-ion secondary batteries, components for optical filters with functions such as light diffusion / reflection / anti-reflection, high-performance adhesives for sintered porous bodies such as ceramics, pore-imparting materials such as breathable membranes, carriers for immobilizing immunochemically active substances, sintered filters with fine pores / high specific surface area, slip-imparting agents, colorants, matting agents for coatings, light diffusion additives, insulating fillers, crystal nucleating agents, chromatographic fillers, and carriers for immunodiagnostic drugs.

[0005] In such applications of functional new materials, there is a strong demand for spherical polyethylene ultrafine particles with smaller particle size, narrower particle size distribution, and no agglomeration between particles in order to further develop functions and improve performance and quality.

[0006] On the other hand, polyolefin microparticles are difficult to polymerize using water, such as emulsion polymerization, and it is generally difficult to control the shape of the resulting polymer. The methods for producing polyethylene microparticles known to date can be roughly divided into the following four methods: (1) mechanical pulverization (normal temperature / freeze pulverization, wet pulverization, jet pulverization), (2) spraying (drying, coagulation), (3) forced emulsification (melt emulsification, solution emulsification), and (4) suspension polymerization.

[0007] Mechanical pulverization is a method of directly applying pulverizing energy, such as impact force or shear force, to a bulk polymer to form microparticles. The particles obtained by this method are generally amorphous, making it difficult to obtain polyethylene microparticles with a narrow particle size distribution.

[0008] Secondly, the spraying method is to be dissolved with the polymer solution obtained by block polyethylene in a solvent, the liquid material such as molten polymer after spraying from a nozzle, and then solidified by drying, cooling, and the method for obtaining polymer particles. The polyethylene particles obtained by this method become the microparticles with high sphericity due to the surface tension of the liquid material ejected, but are mostly obtained in the form of agglomerates of several particles, and usually have a wide particle size distribution. In addition, according to the molecular weight of the polyethylene resin, the viscosity of the polymer solution sometimes becomes higher and wire drawing etc. occurs when spraying and cannot be sprayed into microparticles. Therefore, the spraying method exists and is difficult to be applied to the tendency of the polyethylene resin of (super) high molecular weight.

[0009] In contrast, the emulsification method is a method in which a polyethylene resin is forcibly emulsified in an aqueous medium in the presence of an emulsifier or a dispersant at a temperature above the melting point. However, due to shearing of the molten polymer in the aqueous medium, the method has the advantage of easily obtaining spherical polyethylene particles with few agglomerated particles compared to the above-mentioned two micronization methods. However, as the molecular weight of the polyethylene resin increases, this method also makes it difficult to maintain a narrow particle size distribution, and thus has the tendency to be difficult to be applied to ultra-high molecular weight polyethylene. In addition, there are also problems such as the emulsifier used remaining in the microparticles, and sometimes applications are restricted.

[0010] The present applicant has reported a method for producing spherical polyethylene microparticles directly from ethylene monomer by polymerization using a solid olefin polymerization catalyst with controlled-shape microparticles. (Patent Documents 1 to 4)

[0011] These methods are methods for obtaining polyolefin microparticles by utilizing the so-called replication effect, in which the particle shape and particle size distribution of the solid olefin polymerization catalyst component are directly reflected in the shape and particle size distribution of the produced polyethylene microparticles.

[0012] Prior art literature

[0013] Patent Literature

[0014] Patent Document 1: Japanese Patent No. 4828432

[0015] Patent Document 2: Japanese Patent No. 5221848

[0016] Patent Document 3: Japanese Patent Application Laid-Open No. 2006-206768

[0017] Patent Document 4: Japanese Patent Application Laid-Open No. 2006-206769 Summary of the Invention

[0018] Problems to be solved by the invention

[0019] Patent Documents 1 to 4 disclose in their examples that magnesium compound particles having an average particle size of 0.95 to 20 μm can be obtained as a carrier for obtaining a solid olefin polymerization catalyst, that is, magnesium compound particles.

[0020] According to the research conducted by the present inventors, when attempting to produce smaller magnesium compound particles, when using these particles to prepare a solid olefin polymerization catalyst and then conducting olefin polymerization, sometimes spherical particles with smooth surfaces are produced, and sometimes olefin polymer particles with a shape similar to so-called konpeito, which are substantially spherical but have some irregularities on the surface, are produced.

[0021] Generally speaking, though it is believed that spherical microparticles also depend on particle size distribution, particle mobility sometimes decreases.For example, when transferring particles via pipes, etc., sometimes, a vaulted particle aggregate shape is formed and particle mobility is lost.On the other hand, the surface has concavoconvex particles, which is sometimes advantageous in terms of particle mobility, compared with spherical particles.In addition, according to aforesaid purposes, sometimes it is also divided into the situation that thinks that spherical particles are suitable and the situation that thinks that the surface has concavoconvex particles is suitable.

[0022] In other words, it is believed that in the case of the emulsion polymerization method, spherical particles are formed according to the laws of physics. On the other hand, it is known that it is sometimes difficult to stably produce olefin polymer particles with a specific shape (such as the aforementioned surface irregularity) within a specific particle size range.

[0023] Therefore, an object of the present invention is to provide a method for producing magnesium compound particles useful for stably producing the above-mentioned olefin polymer particles having an uneven surface (hereinafter sometimes referred to as "particles α").

[0024] Another object of the present invention is to provide a method for stably and selectively producing olefin polymer particles (hereinafter sometimes referred to as "particles β") having smooth surfaces and the aforementioned particles α (a method for controlling particle shape).

[0025] Furthermore, an object is to provide olefin polymer particles (hereinafter sometimes referred to as "particles α1") that satisfy specific requirements.

[0026] Means for solving problems

[0027] The present inventors have conducted research and discovered that magnesium compound particles useful for producing olefin polymer particles having a surface irregularity can be obtained by producing particles having a specific molar ratio of magnesium atoms to atoms of metal elements selected from Groups 1, 2, and 13 of the Periodic Table (excluding magnesium) within a specific particle size range. The method comprises contacting a magnesium-containing compound with a compound containing atoms of an element selected from Groups 1, 2, and 13 of the Periodic Table within a specific temperature range. Furthermore, the present inventors discovered that by controlling the molar ratio within a specific range, selective production control of the aforementioned "particles α" and "particles β" can be achieved. Furthermore, the present inventors discovered novel olefin polymer particles (particles α1) that meet a specific pore volume range determined by mercury porosimetry, thereby completing the present invention. The present invention is defined by the following requirements. [1]

[0029] A method for producing magnesium compound particles, comprising a contacting step of bringing a magnesium compound-containing solution (A) into contact with an organometallic compound (B) at a temperature ranging from -20°C to 10°C.

[0030] The magnesium compound-containing solution (A) comprises:

[0031] (A-1) a magnesium-containing compound, and

[0032] (A-2) a compound containing an element selected from Group 15 and Group 16 elements of the periodic table;

[0033] The organometallic compound (B) contains a metal element (MB) selected from the group consisting of elements of Groups 1, 2, and 13 of the periodic table (excluding magnesium).

[0034] Furthermore, the magnesium compound particles satisfy the following requirements (i) and (ii):

[0035] (i) The particle size is 0.05 to 0.90 μm.

[0036] (ii) The ratio of the molar content of magnesium atoms [Mg] to the molar content of atoms of the metal element (MB) [MB] ([Mg] / [MB]) is 1.0 or more and 11.5 or less. [2]

[0038] The production method according to the above [1], wherein the ratio ([MBr] / [Mgr]) of the molar amount [MBr] of the atoms of the metal element (MB) used in the contact step to the molar amount [Mgr] of magnesium atoms contained in the magnesium compound-containing solution (A) is 2.5 to 2.96. [3]

[0040] The production method according to [1] or [2], wherein, in the contact step, the time for contacting the magnesium compound-containing solution (A) and the organometallic compound (B) is 0.6 to 10 hours. [4]

[0042] The production method according to any one of [1] to [3], wherein the [Mg] / [MB] is 5.0 to 11.3. [5]

[0044] The production method according to any one of [1] to [4], wherein the magnesium compound-containing solution (A) further contains (A-3) a liquid hydrocarbon compound. [6]

[0046] A method for controlling the shape of olefin polymer particles, comprising:

[0047] a contacting step of bringing a magnesium-containing compound solution (A) into contact with an organometallic compound (B) at a temperature range of -20°C to 10°C, wherein the magnesium-containing compound solution (A) comprises (A-1) a magnesium-containing compound and (A-2) a compound comprising an element selected from Groups 15 and 16 of the periodic table, and the organometallic compound comprises (B) a metal element (MB) selected from Groups 1, 2, and 13 of the periodic table (excluding magnesium); and

[0048] a step of polymerizing olefins in the presence of an olefin polymerization catalyst comprising magnesium compound particles having a particle size of 0.05 to 0.90 μm produced in the contact step and a transition metal compound component to produce olefin polymer particles;

[0049] The ratio ([Mg] / [MB]) of the molar content of magnesium atoms [Mg] in the magnesium compound particles to the molar content of atoms of the metal element (MB) [MB] is controlled within a range of 1.0 to 20. [7]

[0051] An olefin polymer particle having an average particle size of 3 to 25 μm,

[0052] The intrinsic viscosity [η] in decalin at 135°C is 5 to 50 dl / g,

[0053] The pore volume of the pores with a diameter of 0.1 to 1 μm determined by mercury porosimetry is 25 to 100 mm 3 / g.

[0054] Effects of the Invention

[0055] The method for producing magnesium compound particles of the present invention can provide magnesium compound particles useful for producing olefin polymer particles (particles α) having an uneven surface in a specific region having a small particle size.

[0056] Furthermore, according to the control method of the present invention, olefin polymer particles (particles β) having smooth surfaces and the aforementioned particles α can be selectively produced stably.

[0057] Such magnesium compound particles are expected to be suitably used as a support for a catalyst for olefin polymer particles.

[0058] The olefin polymer particles (α1) of the present invention are olefin polymer microparticles satisfying specific ranges of particle size, intrinsic viscosity, and pore volume value measured by mercury porosimetry. Olefin polymer particles (α1) satisfying these requirements are expected to also have excellent particle flowability. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] [ Figure 1 ] Figure 1 This is an electron microscope photograph of the polymer particles used in Example 21.

[0060] [ Figure 2 ] Figure 2 This is an electron microscope photograph of the polymer particles used in Example 22.

[0061] [ Figure 3 ] Figure 3 This is an electron microscope photograph of the polymer particles used in Comparative Example 21.

[0062] [ Figure 4 ] Figure 4 This is an electron microscope photograph of the polymer particles used in Comparative Example 22. DETAILED DESCRIPTION

[0063] The method for producing the magnesium compound particles of the present invention is determined as follows.

[0064] A method for producing magnesium compound particles, comprising a contacting step of bringing a magnesium compound-containing solution (A) into contact with an organometallic compound (B) at a temperature range of -20°C to 10°C, wherein the magnesium compound-containing solution (A) comprises (A-1) a magnesium-containing compound and (A-2) a compound comprising an element selected from Groups 15 and 16 of the periodic table, and the organometallic compound (B) comprises a metal element (MB) selected from Groups 1, 2, and 13 of the periodic table (excluding magnesium).

[0065] The magnesium compound particles satisfy the following requirements (i) and (ii):

[0066] (i) The particle size is 0.05 to 0.90 μm.

[0067] (ii) The molar content ratio of the magnesium atom content [Mg] to the molar content of the metal element (MB) atoms [MB] ([Mg] / [MB]) is 1.0 or more and 11.5 or less.

[0068] Hereinafter, the above-mentioned manufacturing method will be described in detail.

[0069] [Method for producing magnesium compound particles]

[0070] The magnesium compound particles produced by the production method of the present invention (hereinafter also referred to as "magnesium compound particles of the present invention") are particles containing magnesium and a metal element (MB) selected from Groups 1, 2, and 13 of the periodic table (excluding magnesium), and have an average particle size of 0.05 to 0.90 μm. The preferred lower limit of the average particle size is 0.10 μm, more preferably 0.20 μm, and even more preferably 0.25 μm. On the other hand, the preferred upper limit is 0.85 μm, more preferably 0.80 μm, and even more preferably 0.75 μm.

[0071] The particles preferably contain an alkoxy group having 1 to 20 carbon atoms and are preferably insoluble in hydrocarbon solvents.

[0072] The aforementioned (A) magnesium compound solution (hereinafter also referred to as "(A) component" or "(A) magnesium compound liquid") contains (A-1) a magnesium-containing compound and (A-2) a compound containing an element selected from Group 15 and Group 16 elements of the periodic table.

[0073] As the above-mentioned magnesium-containing compound (A-1), known magnesium compounds such as organomagnesium compounds represented by halogen-containing magnesium, alkoxy-containing magnesium, magnesium salts of carboxylic acids, and Grignard reagents can be used. In addition, the aforementioned magnesium compounds can also be used in combination, or can be used after reacting with halogens etc. midway. The aforementioned magnesium compound is preferably halogen-containing magnesium, more preferably a magnesium halide. As specific magnesium halides, magnesium chloride and magnesium bromide are preferably used. Such magnesium halides can be used directly as commercial products, or can be prepared separately from alkyl magnesiums. In the latter case, it is also possible to use without isolating the magnesium halide.

[0074] The compound (A-2) containing an element selected from Group XV and Group XVI of the periodic table is not particularly limited as long as it is a compound capable of forming a solution, such as an alcohol, phenol, ether, carboxylic acid, amine, or organic phosphorus compound, but is preferably a compound having a hydroxyl group.

[0075] More specifically, alcohols or phenol compounds having 1 to 20 carbon atoms are preferred.

[0076] Especially preferred are alcohols having 1 to 20 carbon atoms.

[0077] Examples of alcohols and phenols having 1 to 20 carbon atoms include alcohol and phenol compounds corresponding to alkoxy groups having 1 to 20 carbon atoms. Specific examples of the compounds include:

[0078] Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, n-hexanol, n-heptanol, 2-ethyl-1-hexanol, n-octanol, dodecanol, octadecyl alcohol, 2-octyl-1-dodecanol, oleyl alcohol, benzyl alcohol, phenylethanol, cumyl alcohol, isopropylbenzyl alcohol, etc.

[0079] Halogen-containing alcohols such as trichloromethanol, trichloroethanol, and trichlorohexanol,

[0080] Phenol, cresol, ethylphenol, nonylphenol, cumylphenol, naphthol and other phenols containing lower alkyl groups,

[0081] Among them, methanol, ethanol, propanol, butanol, pentanol, isopentanol, hexanol, heptanol, 2-ethyl-1-hexanol, octanol, dodecanol, and 2-octyl-1-dodecanol are preferred.

[0082] As a preferred method for contacting the magnesium-containing compound (A-1) with the compound (A-2) containing an element selected from Groups 15 and 16 of the periodic table, the contact is carried out in the presence of a liquid hydrocarbon compound. Examples of such hydrocarbon compounds include:

[0083] Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene;

[0084] Alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane;

[0085] Aromatic hydrocarbons such as benzene, toluene, and xylene;

[0086] Halogenated hydrocarbons such as dichloroethane, chlorobenzene, dichloromethane, or mixtures thereof.

[0087] As such a hydrocarbon solvent, aliphatic saturated hydrocarbons are often preferably used mainly from the viewpoint of safety.

[0088] The above-mentioned contact is usually carried out under heating. During heating, the temperature can be arbitrarily selected up to the boiling point of the solvent used. The contact time also depends on the contact temperature. For example, when n-decane is used as the solvent and the heating temperature is 130°C, after about 4 hours of contact, the contents show a homogenization phenomenon, which is a sign that the contact is complete. During the contact, it is usually carried out using a device that promotes contact by stirring, etc. At the beginning of the contact, the system is usually non-uniform, but as the contact proceeds, the contents gradually become homogenized and eventually liquefy.

[0089] When the magnesium compound particles of the present invention are used as a support for a solid catalyst component in producing ethylene polymer particles, a production method that involves complete liquefaction is preferred from the viewpoint of the powder properties of the ethylene polymer particles obtained by polymerization.

[0090] The (A) magnesium compound liquid thus prepared may be used after removing the solvent used during the contacting or may be used without distilling off the solvent. Usually, the liquid is supplied to the next step without distilling off the solvent.

[0091] The method for producing magnesium compound particles of the present invention comprises a contacting step of bringing the above-mentioned (A) magnesium compound liquid into contact with (B) an organometallic compound (hereinafter also referred to as "(B) component") containing a metal element (MB) selected from elements of Groups 1, 2, and 13 of the periodic table (excluding magnesium).

[0092] (B) The organometallic compound includes organic alkali metal compounds such as butyllithium, and the following aluminum-containing compounds are industrially preferred.

[0093] AYR n X 3-n ···(1)

[0094] In the general formula (1), R is a hydrocarbon group having 1 to 20 carbon atoms, specifically, methyl, ethyl, propyl, butyl, hexyl, octyl, and decyl. X represents a halogen atom such as a chlorine atom or a bromine atom, or a hydrogen atom. n represents a real number of 1 to 3, preferably 2 or 3. When R is multiple, each R may be the same or different, and when X is multiple, each X may be the same or different. As the organoaluminum compound, specifically, the following compound is used. That is, as the organoaluminum compound that meets the above requirements, the following can be exemplified:

[0095] Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri(2-ethylhexyl)aluminum;

[0096] Alkenyl aluminum such as isoprene aluminum; dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, and dimethyl aluminum bromide;

[0097] Sesquialkylaluminum halides such as sesquimethylaluminum chloride, sesquiethylaluminum chloride, sesquiisopropylaluminum chloride, sesquibutylaluminum chloride, and sesquiethylaluminum bromide;

[0098] Alkyl aluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, and ethylaluminum dibromide;

[0099] Alkyl aluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride are preferred. Among them, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, and diisobutylaluminum hydride are preferred.

[0100] One of the key points of the present invention lies in the contact method and contact conditions. Specifically, a method in which the (A) magnesium compound liquid and the (B) organometallic compound are brought into contact while being mixed at high speed under strong shearing force is preferred. The apparatus used for high-speed mixing of the magnesium compound liquid (A) is not particularly limited as long as it is a commercially available apparatus generally used as an emulsifier or disperser. Examples thereof include batch emulsifiers such as Ultra-Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto-Homomixer (manufactured by Tokushiki Kagaku Kogyo Co., Ltd.), TK Neo-Mixer (manufactured by Tokushiki Kagaku Kogyo Co., Ltd.), and National Cooking Mixer (manufactured by Matsushita Electric Industrial Co., Ltd.); continuous emulsifiers such as Ebara Milder (manufactured by Ebara Seisakusho Co., Ltd.), TK Pipeline-Homomixer, TK Homomic Line Flow (manufactured by Tokushiki Kagaku Kogyo Co., Ltd.), colloid mill (manufactured by Nippon Seiki Co., Ltd.), slusher, triangular wet fine pulverizer (manufactured by Mitsui Miike Chemical Industry Co., Ltd.), Cavitron (manufactured by Eurotec), and Fine Flow Mill (manufactured by Pacific Machinery Industry Co., Ltd.); and continuous emulsifiers such as CLEARMIX (M Technique Co., Ltd.), FILMIX (Tokushu Kikka Kogyo Co., Ltd.), and other intermittent or continuous dual-purpose emulsifiers; Microfluidizer (Mizuho Kogyo Co., Ltd.), Nanomaker, Nanomizer (Nanomizer Co., Ltd.), APVGaulin (Gaulin Co., Ltd.), and other high-pressure emulsifiers; Membrane emulsifier (Lenghua Kogyo Co., Ltd.), and other membrane emulsifiers; Vibration emulsifiers such as VIBROMIXER (Lenghua Kogyo Co., Ltd.); Ultrasonic emulsifiers such as Ultrasonic Homogenizer (Branson Co., Ltd.), etc.

[0101] When the magnesium compound liquid (A) contacts the organometallic compound (B), the magnesium compound liquid (A) is preferably in the form of a solution containing a hydrocarbon liquid as described above. The organometallic compound (B) can be diluted in a solvent before use. Typically, it is used as a solution diluted in an aliphatic saturated hydrocarbon such as n-decane or n-hexane, or an aromatic hydrocarbon solvent such as toluene or xylene. As such hydrocarbon solvents, aliphatic saturated hydrocarbons are often preferred, primarily from the perspective of safety.

[0102] In the present invention, a method of adding (B) the organometallic compound to (A) the magnesium compound liquid is a preferred method.

[0103] The above-mentioned contact step is usually preferably carried out for 0.6 hours to 10 hours. If the heat removal capacity in the contact system is sufficient, the addition can be completed in a short time. On the other hand, if the capacity is insufficient, it is better to add for a long time. The addition of the organoaluminum compound can be added all at once or divided into several batches. In this case, it is preferable to set a step of bringing them into contact at a temperature range of -20°C to 10°C. In particular, when initially bringing (A) the magnesium compound liquid into contact with (B) the organometallic compound, it is preferably carried out within the above-mentioned temperature range. In most cases, including such a step is conducive to stably obtaining particles with a small particle size. In addition, in the contact at the above-mentioned temperature, the molar ratio ([MB] / [Mg]) of the amount of magnesium atoms [Mg] in the (A) magnesium compound liquid to the amount of atoms of the metal element (MB) [MB] in the (B) organometallic compound is preferably in the range of 0.9 to 1.2. The more preferred lower limit is 1.00, and the more preferred upper limit is 1.17, and the more preferred upper limit is 1.15.

[0104] Furthermore, regarding the amounts of the (A) magnesium compound liquid and the (B) organometallic compound used in the entire contact step of the (A) magnesium compound liquid and the (B) organometallic compound, the molar ratio ([MBr] / [Mgr]) of the amount of magnesium atoms [Mgr] in the (A) magnesium compound liquid to the amount of atoms of the metal element (MB) [MBr] in the (B) organometallic compound is preferably 2.5 to 2.96. The lower limit is more preferably 2.60, further preferably 2.70, and particularly preferably 2.80.

[0105] A preferred embodiment of the contact step of the (A) magnesium compound liquid and the (B) organometallic compound is described below.

[0106] As for the contact between the (A) magnesium compound liquid and the (B) organometallic compound represented by the general formula (1), the preferred embodiment is particularly described in which an organoaluminum compound is used as the (B) organometallic compound. For example, a method based on the reaction of two liquid substances such as contacting a hydrocarbon-diluted solution of the magnesium compound with an organoaluminum compound diluted in a hydrocarbon solvent is preferred. The particles generated at this time sometimes have different shapes and sizes depending on their formation conditions, but in order to obtain a solid product with a uniform shape and particle size, it is preferred to avoid rapid particle formation reactions while maintaining high shear and high-speed mixing as described above. For example, when the magnesium compound and the organoaluminum compound are contacted and mixed with each other in a liquid state and react with each other to form a solid product, it is preferred to mix the two at a low temperature at which solids are not rapidly generated due to their contact, and then increase the temperature to gradually form a solid product. According to this method, it is easy to control the particle size of the solid product in the ultrafine particle region, and it is easy to obtain an ultrafine and spherical solid product with an extremely narrow particle size distribution.

[0107] The average particle size of the magnesium compound particles obtained by the above-mentioned method can be increased or decreased by, for example, adjusting the mixing speed during the high-speed mixing in the above-mentioned contact step.

[0108] By using a solid polymerization catalyst component using the magnesium compound particles of the present invention as a support for a polymerization catalyst, olefin polymer particles such as ethylene polymer particles can be produced that are (substantially) spherical but have surface irregularities.

[0109] The magnesium compound particles obtained by the above method contain magnesium atoms [Mg] derived from the magnesium compound liquid (A) and atoms [MB] derived from the metal element (MB) of the organometallic compound (B). The composition (molar ratio) of the magnesium atoms [Mg] / (molar content of the metal element (MB) atoms [MB]) is 1.0 or more and 11.5 or less. The preferred lower limit is 5, more preferably 6, even more preferably 7, and particularly preferably 8. On the other hand, the preferred upper limit is 11.4, more preferably 11.3, and even more preferably 11.2.

[0110] As described below, when a solid olefin polymerization catalyst is prepared using the magnesium compound particles of the present invention and olefins are polymerized in the presence of the catalyst, olefin polymer particles having a surface irregularity can be obtained. Since the magnesium compound particles of the present invention are extremely small, their fine surface shape is often difficult to determine. However, it is speculated that the particles may also have a nearly spherical shape with a surface irregularity. The reason for this shape is not yet clear, but the present inventors speculate as follows.

[0111] Small-sized particles, such as the magnesium compound particles of the present invention, are primarily composed of the magnesium compound in component (A), with components derived from component (B) considered to be foreign matter. The surface shape of these particles is believed to be susceptible to the content of the compound derived from component (B). While the surface tensions of components (A) and (B) naturally differ, a higher content of component (B) is believed to increase the amount of foreign matter, in addition to the influence of the surface tensions of both components. This is thought to facilitate the formation of surface irregularities. This influence is particularly pronounced in the case of small-sized particles.

[0112] In the case of the present invention, since there are relatively many components derived from the MB-containing compound (e.g., an organoaluminum compound), it is believed that not only the surface tension during particle formation but also the particle shape is easily affected when the compound derived from the (B) component, which is a foreign matter, solidifies, and thus particles with relatively many surface irregularities are likely to be obtained.

[0113] In the present invention, magnesium compound particles are produced under conditions where the amount of organometallic compound (B) used is relatively small compared to the amount of magnesium compound liquid (A). However, this results in an unexpectedly high content of metal element (MB) atoms in the magnesium compound particles. This is believed to be because the presence of a high amount of components derived from MB atoms on the particle surface may easily cause surface irregularities. (When the amount of organometallic compound (B) used is high (excessive), it is believed that the excess organometallic compound (B) may wash away the components derived from MB atoms on the surface. In other words, the surface may become smooth.)

[0114] In addition to the above reasons, it is also possible that the influence of the aforementioned component (A-2) may easily result in the formation of olefin polymer particles with a large number of surface irregularities. (In this case, the magnesium compound particles may not have a shape with surface irregularities.)

[0115] When the component (A-2) is an alcohol, the magnesium compound particles of the present invention often contain alkoxy groups (hereinafter sometimes referred to as (RO)). The magnesium compound particles of the present invention tend to contain alkoxy groups (RO) relatively easily. The specific molar ratio of alkoxy groups to magnesium atoms (molar amount of alkoxy groups / molar amount of magnesium atoms, hereinafter also referred to as "[RO] / [Mg]") is preferably 0.22 to 1.0. The more preferred lower limit is 0.23, and even more preferably 0.24. On the other hand, the more preferred upper limit is 0.8, even more preferably 0.6, and particularly preferably 0.55.

[0116] It is speculated that the alkoxy groups often form alkoxide structures bonded to the metal atoms of the component (B). Such alkoxy groups tend to enhance the olefin polymerization activity of the olefin polymerization catalyst described later. Therefore, it is thought that if the alkoxides are abundant and concentrated in the magnesium compound particles, surface irregularities may be easily formed.

[0117] On the other hand, the present inventors have also discovered that when the composition (molar ratio) of magnesium atoms [Mg] derived from the magnesium compound liquid (A) to metal element (MB) atoms [MB] derived from the organometallic compound (B) in the obtained magnesium compound particles is (molar content of magnesium atoms [Mg]) / (molar content of atoms of the metal element (MB) [MB]) exceeding 11.5 and being 20 or less, olefin polymer particles obtained using the obtained magnesium compound particles or an olefin polymerization catalyst containing the magnesium compound particles tend to have smooth spherical particles. The above-mentioned lower limit is preferably 11.6, more preferably 11.7, and even more preferably 11.8. On the other hand, the preferred upper limit is 18, more preferably 17, even more preferably 16, and particularly preferably 15.

[0118] In the case of the above embodiment, since the components derived from the MB-containing compound (e.g., the organoaluminum compound) are relatively small, the influence of surface tension during particle formation is dominant over the compound derived from the (B) component as a foreign matter, and therefore it is thought that particles with relatively smooth surfaces are easily obtained.

[0119] Alternatively, in the case of the above embodiment, since [RO] / [Mg] tends to be low, it is considered that the metal alkoxide sites are less likely to be segregated, and as a result, particles having relatively smooth surfaces may be easily obtained.

[0120] To obtain the magnesium compound particles described above, for example, the contacting step of the magnesium compound liquid (A) and the organometallic compound (B) is preferably performed under conditions such that the molar ratio of the amount of magnesium atoms [Mgr] in the magnesium compound liquid (A) to the amount of metal element (MB) atoms [MBr] in the organometallic compound (B) is 2.97 to 10. A more preferred lower limit is 2.98, and even more preferably 2.99. On the other hand, a more preferred upper limit is 9.0, even more preferably 8.0, and particularly preferably 7.0.

[0121] By utilizing the above-described tendency, by controlling the molar ratio (molar content of magnesium atoms [Mg]) / (molar content of atoms of the metal element (MB) [MB]) within the range of 1.0 to 20, olefin polymer particles having a desired shape can be produced when olefin polymerization is carried out using an olefin polymerization catalyst containing the obtained magnesium compound particles. In other words, the shape of the olefin polymer particles can be controlled.

[0122] As the production conditions for the magnesium compound particles for performing the above-mentioned control, for example, the amounts of the (A) magnesium compound liquid and the (B) organometallic compound used in the entire contact step of the (A) magnesium compound liquid and the (B) organometallic compound are controlled within a range of 2.5 to 10 in terms of the molar ratio ([MBr] / [Mgr]) of the amount of magnesium atoms [Mgr] in the (A) magnesium compound liquid to the amount of atoms of the metal element (MB) [MBr] in the (B) organometallic compound, and the particles are of the target shape.

[0123] Average particle size

[0124] The average particle size (volume average diameter) used in the present invention can be measured by taking images of three arbitrary locations on a sample weighing several grams using a scanning electron microscope (e.g., TM4000, manufactured by Hitachi High-Technologies Corporation). The resulting SEM images are then used to measure the particle size distribution using image analysis software (e.g., MacView, manufactured by Mountech). This method can be applied to the aforementioned magnesium compound particles and the olefin polymer particles described below.

[0125] When the particle size of the magnesium compound microparticles is too small, the particle size and polymerization activity of the olefin polymer obtained using an olefin polymerization catalyst containing the magnesium compound can be calculated using conventional methods. This method is based on the empirical rule that the shape of the solid polymer particles obtained by polymerizing olefins using a solid olefin polymerization catalyst will be (substantially) similar to the shape of the solid olefin polymerization catalyst. Therefore, the production method, production conditions, and shape control of the olefin polymerization catalyst are of great significance as a method for controlling the shape of the olefin polymer particles.

[0126] The magnesium compound particles of the present invention can be loaded with an olefin polymerization catalyst to form a solid olefin polymerization catalyst. Furthermore, olefin polymers can be produced by polymerizing olefins using the catalyst. In this case, the resulting olefin polymers, while also depending on the amount of olefin polymerized, are likely to have small particle sizes.

[0127] The expected olefin polymer particles (particularly ethylene polymer particles (hereinafter also referred to as “ethylene polymer particles of the present invention”)) and the olefin polymerization catalyst are described below.

[0128] [Ethylene polymer particles]

[0129] Preferred examples of ethylene polymer particles obtained using the olefin polymerization catalyst of the present invention include the following.

[0130] This method has the following characteristics: the intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.1 to 50 dl / g, at least 95% by weight or more passes through a sieve with a mesh size of 37 μm, and the average particle size (d) is 3 μm≤d≤25 μm.

[0131] Hereinafter, the method for measuring the properties of the particles specified in each requirement and the method for producing the particles will be described.

[0132] Intrinsic viscosity [η]

[0133] The above-mentioned intrinsic viscosity [η] is a value measured using decalin solvent at 135°C. That is, about 20 mg of the granulated pellets were dissolved in 15 ml of decalin and the specific viscosity η was measured in an oil bath at 135°C. SP 5 ml of decalin solvent was added to the decalin solution to dilute it, and the specific viscosity η was measured in the same manner. SP Repeat this dilution operation twice more and find the η when the concentration (C) is extrapolated to 0. SP The value of / C is taken as the intrinsic viscosity [η].

[0134] [η]=lim(η SP / C), (C→0)

[0135] The intrinsic viscosity [η] of the ethylene polymer particles of the present invention needs to be in the range of 0.1 to 50 dl / g, preferably 0.15 to 50 dl / g, and more preferably 0.2 to 50 dl / g. Ethylene polymer particles having an intrinsic viscosity [η] greater than 0.1 dl / g are unlikely to partially melt the polymer particles due to heat generation during polymerization, or to dissolve a portion of the generated polymer into the polymerization solvent during slurry polymerization. Therefore, it is expected that the polymer particle shape will not be destroyed, nor will the polymer particles be agglomerated.

[0136] Furthermore, when the intrinsic viscosity [η] is 5 dl / g or greater, more preferably 6 dl / g or greater, and even more preferably 10 dl / g or greater, excellent wear resistance, impact resistance, and self-lubricating properties are achieved. Furthermore, ultrahigh molecular weight olefin polymers having an intrinsic viscosity [η] of 5 dl / g or greater tend to be difficult to produce into microparticles using emulsification methods or the like.

[0137] The throughput of the sieve with a mesh size of 37 μm

[0138] For the ethylene polymer particles obtained by the aforementioned olefin polymerization catalyst of the present invention, use vibratory screen or ultrasonic vibratory screen, preferably more than 95 % by weight by the sieve (Tyler#400) of mesh size 37 μm, more preferably by more than 98 % by weight, further preferably by more than 99.7 % by weight, most preferably by 100 % by weight. That is, the amount of the ethylene polymer particles more than 95 % by weight refers to that the amount of coarse particles is few. For such polymer particles, can not cause flowability, dispersibility to reduce owing to the existence of coarse particles, hinder the ideal closest filling as the filler of powder.

[0139] Average particle size

[0140] The average particle size (volume average diameter) used in the present invention can be measured as follows: using a scanning electron microscope (e.g., TM4000 scanning electron microscope manufactured by Hitachi High-Tech Corporation), images of any three locations in a measurement sample weighing several grams are taken, and the obtained SEM photographs are measured using image analysis particle size distribution measurement software (e.g., MacView manufactured by Mountech).

[0141] As described above, when the particle size of the magnesium compound particles is too small, it can be calculated by a conventional method based on the particle size and polymerization activity of the olefin polymer obtained using the olefin polymerization catalyst containing the magnesium compound particles.

[0142] The average particle size (d) of the ethylene polymer particles obtained using the olefin polymerization catalyst of the present invention is preferably 3 μm ≤ d ≤ 25 μm. The more preferred upper limit is 20 μm, and more preferably 15 μm. On the other hand, the more preferred lower limit is 4 μm, and more preferably 5 μm. A generally preferred range is 3 to 15 μm, and more preferably 3 μm ≤ d ≤ 10 μm.

[0143] If the average particle size of the ethylene polymer particles is more than 3 μm, the processing during molding is easier, and the surrounding environment is not easily contaminated by particles. Therefore, even if used in the manufacturing process of various precision instruments, sanitary products, etc., the control of the poor quality caused by environmental pollution is also easy.

[0144] Furthermore, since the possibility of adhesion to clothing or inhalation is reduced, it is also excellent in ensuring a safe working environment. Furthermore, it is relatively easy to handle during compression molding of sintered filters, etc., and has excellent mold sealing properties, so filters with uniform pore sizes can be efficiently produced.

[0145] Furthermore, if the average particle size is 25 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, and particularly preferably 10 μm or less, the particles have a large specific surface area per unit mass, making them suitable for use as fillers, adsorbents, and catalyst supports in columns for efficient separation of chemical and biological substances. Furthermore, the properties of the ethylene-based polymer particles influence their physical properties after molding. In addition to enabling the production of filters with small pore sizes as raw materials for sintered filters, they can also provide a favorable feel on the skin as raw materials for cosmetics.

[0146] The olefin polymer particles α1 according to one embodiment of the present invention are novel olefin polymer particles having an average particle size of 3 to 25 μm and an intrinsic viscosity [η] of 5 to 50 dl / g. Furthermore, the particles are characterized by having a pore volume corresponding to pores with a pore diameter of 0.1 to 1 μm, as measured by mercury porosimetry, of 25 to 100 mm. 3 / g. However, the present inventors believe that the pore volume in the present invention is a special parameter that includes values ​​derived from the pores and also values ​​derived from the measured surface irregularities of the particles. This is strongly inferred based on the shapes of the olefin polymer particles in the electron micrographs of the Examples shown in the accompanying drawings and the pore volume results described above.

[0147] Regarding the surface morphology of the olefin polymer particles α1 of the present invention, as shown in the aforementioned electron microscope photograph magnified 1000x or more, preferably 30% or more, and more preferably 50% or more, of the particles observed within any 100 μm square area have five or more protrusions observed on half the particle surface. In the present invention, the protrusions are defined as having a width (the width of the thickest portion of each protrusion) of 1 / 100 to 1 / 3 the diameter of the olefin polymer particle.

[0148] The mercury porosimetry measurement is performed using a mercury porosimeter (e.g., trade name: PoreMaster 60GT, manufactured by Quantachrome) using conventional methods. The pore volume value is determined by analyzing the measurement data using analysis software provided with the instrument (e.g., trade name: PoreMaster for Windows) and by accumulating the volume of pores with a diameter of 0.1 to 1 μm.

[0149] The electron micrographs are obtained by observation and photography using, for example, a TM4000 Plus scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) by conventional methods.

[0150] The ethylene polymer particles of the present invention are characterized by comprising: 90 to 100 mol% of structural units derived from ethylene; and 0 to 10 mol% of structural units derived from one or more monomers selected from linear or branched α-olefins having 3 to 6 carbon atoms, cyclic olefins, polar group-containing olefins, dienes, trienes, and aromatic vinyl compounds. Examples of the linear or branched α-olefins having 3 to 6 carbon atoms include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-pentene. Among them, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene are preferred.

[0151] Examples of the cyclic olefin include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

[0152] Examples of the polar group-containing olefin include:

[0153] α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride, and their metal salts of α,β-unsaturated carboxylic acids such as their sodium, potassium, lithium, zinc, magnesium, and calcium salts;

[0154] α,β-unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate;

[0155] Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate;

[0156] Unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc.

[0157] Examples of the dienes and trienes include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-tridecene.

[0158] Examples of the aromatic vinyl compound include:

[0159] Monoalkyl or polyalkyl styrenes such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene;

[0160] Styrene derivatives containing functional groups, such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, and divinylbenzene;

[0161] 3-Phenylpropylene, 4-phenylpropylene, α-methylstyrene, etc., and one or more of them can be used.

[0162] Hereinafter, the method for producing the ethylene-based polymer particles (bulk) of the present invention will be described.

[0163] The ethylene polymer particles of the present invention are produced by homopolymerizing ethylene or copolymerizing ethylene with one or more monomers selected from linear or branched α-olefins having 3 to 6 carbon atoms, cyclic olefins, polar group-containing olefins, dienes, trienes, and aromatic vinyl compounds using the magnesium compound particles of the present invention described below as a support component of a solid catalyst component for polymerization.

[0164] [Method for producing ethylene polymer particles]

[0165] Hereinafter, the method for producing the ethylene polymer particles of the present invention will be described in further detail.

[0166] The ethylene polymer particles of the present invention can be obtained by polymerizing ethylene alone or with at least one monomer selected from linear or branched α-olefins having 3 to 6 carbon atoms, cyclic olefins, polar group-containing olefins, dienes, trienes, and aromatic vinyl compounds in the presence of a polymerization catalyst component.

[0167] The polymerization catalyst component is composed of the following substances:

[0168] A solid catalyst component comprising a transition metal compound or (preferably) a liquid titanium compound supported on magnesium compound particles of the present invention,

[0169] Organometallic compounds, and

[0170] Further nonionic surfactants are provided as desired.

[0171] Hereinafter, the solid catalyst component will be described first.

[0172] In the present invention, "supported" means that even when stirred at room temperature under normal pressure for 1 minute to 1 hour in at least one solvent selected from hexane, decane and toluene, the amount of the transition metal compound or the liquid titanium compound dissolved in the solvent is 1% by weight or less each.

[0173] The transition metal compound used for preparing the solid catalyst component using the magnesium compound particles of the present invention, that is, the magnesium-containing support component, is not particularly limited, and for example, those disclosed in the following documents can be used.

[0174] 1) Japanese Patent Application No. 11-315109

[0175] 2) Japanese Patent Application No. 2000-239312

[0176] 3) European Patent Application Publication No. 1008595

[0177] 4) International Publication No. 01 / 55213

[0178] 5) Japanese Patent Application No. 2001-2731

[0179] 6) European Patent Application Publication No. 1043341

[0180] 7) International Publication No. 98 / 27124

[0181] 8)Chemical Review 103,283(2003)

[0182] 9)Bulletin of the Chemical Society of Japan 76,1493(2003)

[0183] 10) Angewandte Chemie, International Edition.English 34(1995)

[0184] 11)Chemical Review 8,2587(1998)2587

[0185] In order to load the transition metal compound on the magnesium compound particles of the present invention, it is sufficient to stir and mix the magnesium compound particles and the transition metal compound in an inert solvent for a predetermined time and then filter them out. A heating operation may also be performed at this time. Examples of inert solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic saturated hydrocarbons such as hexane, heptane, and decane, alicyclic hydrocarbons such as cyclohexane and methylcyclopentane, halogenated hydrocarbons such as acetyl chloride, chlorobenzene, and dichloromethane, or mixtures thereof. The temperature during heating depends on the solvent used and is generally a temperature above the freezing point of the solvent to 200°C, preferably up to 150°C. The stirring and mixing time also depends on the temperature and is generally 30 seconds to 24 hours, preferably 10 minutes to 10 hours. Filtration can be performed using the filtration method used in conventional organic manufacturing chemistry. The filter cake component after filtration can be washed with the aromatic hydrocarbons and aliphatic hydrocarbons exemplified above as needed.

[0186] As the aforementioned transition metal compound component, compounds having the following structures can be mentioned as preferred examples.

[0187] [Chemistry 1]

[0188]

[0189] [wherein, M represents Zr or Hf, m represents an integer of 1 or 2, A represents a 6-membered hydrocarbon ring having one or more alkyl substituents at the 2-position, which may be saturated or unsaturated, R 1 ~R 5may be the same as or different from each other and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, two or more of which may be linked to each other to form a ring,

[0190] In addition, when m is 2, R 1 ~R 5 Two of the groups shown may be linked (however, R 1 (4-m) is a number that satisfies the valence of M, X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and the multiple groups represented by X may be the same as or different from each other, and the multiple groups represented by X may be bonded to each other to form a ring.]

[0191] As the transition metal compound that can be used in the present invention, known compounds can be used without limitation, and examples thereof include the compounds disclosed as specific examples in Patent Documents 1 and 2. Some of them are described below.

[0192] [Chemistry 2]

[0193]

[0194] [Chemistry 3]

[0195]

[0196] [Chemistry 4]

[0197]

[0198] [Chemistry 5]

[0199]

[0200] In the formula, Adm represents an adamantyl group.

[0201] In addition, the transition metal compound may be a compound represented by the following general formula (8). 1 ) i (Pz 2 ) 3-i MY m Z n (8)

[0202] In the above general formula (8), RQ(Pz 1 ) i (Pz 2 ) 3-iis a tridentate anionic ligand or a neutral ligand, and R represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Examples of the halogen atom, the hydrocarbon group, the heterocyclic compound residue, the oxygen-containing group, the sulfur-containing group, the nitrogen-containing group, the boron-containing group, the aluminum-containing group, the phosphorus-containing group, the halogen-containing group, the silicon-containing group, the germanium-containing group, and the tin-containing group include the groups exemplified in the description of X in the general formula (7).

[0203] In the above general formula (8), Q represents a tetravalent group selected from the group consisting of boron, carbon, silicon, germanium, tin and lead, and boron, carbon and silicon are particularly preferred.

[0204] In the above general formula (8), Pz 1 It is a pyrazolyl group substituted at least 3 positions with an unsubstituted aryl group (Aryl), a substituted aryl group (Aryl), an alkyl group having 3 or more carbon atoms, a cycloalkyl group, an amino group, or an oxyalkyl group. Examples of the unsubstituted aryl group (Aryl) include phenyl, naphthyl, and fluorenyl. Examples of the substituted aryl group (Aryl) include groups in which one or more ring hydrogen atoms of the unsubstituted aryl group (Aryl) are replaced with an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms. Preferred Pz 1 The 3-position is substituted with 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 2,3,4,5,6-pentamethylphenyl or 4-tert-butyl-2,6-dimethylphenyl, and the 3-position is particularly preferably substituted with 2,4,6-trimethylphenyl.

[0205] Pz 2 As a substituted pyrazolyl group, it can be combined with the above-mentioned Pz 1 Similarly, the pyrazolyl group may be substituted at any position other than the 3-position with a group exemplified as a substituent for the substituted aryl group.

[0206] In the above general formula (8), M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, specifically, a Group 3 metal atom of scandium, yttrium, lanthanides, and actinides; a Group 4 metal atom of titanium, zirconium, and hafnium; a Group 5 metal atom of vanadium, niobium, and tantalum; a Group 6 metal atom of chromium, molybdenum, and tungsten; a Group 7 metal atom of manganese, technetium, and rhenium; a Group 8 metal atom of iron, ruthenium, and osmium; a Group 9 metal atom of cobalt, rhodium, and iridium; a Group 10 metal atom of nickel, palladium, and platinum; and a Group 11 metal atom of copper, silver, and gold. Among these, Group 3 metal atoms, Group 4 metal atoms, Group 5 metal atoms, and Group 6 metal atoms are preferred, and among these, transition metals such as yttrium, titanium, zirconium, hafnium, vanadium, and chromium are preferred. Furthermore, transition metal atoms of Groups 4 or 5 of the periodic table whose atomic valence state of the transition metal atom M is divalent, trivalent, or tetravalent are further preferred, and titanium, zirconium, hafnium, and vanadium are particularly preferred. When the transition metal atom M is titanium or vanadium, it is particularly preferably trivalent.

[0207] X represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; Y represents a neutral ligand having an electron-donating group; m is a number that satisfies the valence of M; when m is 2 or greater, the multiple atoms or groups represented by X may be the same as or different from each other; the multiple groups represented by X may be bonded to each other to form a ring; and n represents an integer from 0 to 3.

[0208] When X is an oxygen atom, M and X are bonded to each other via a double bond.

[0209] When m is 2 or greater, the multiple atoms or groups represented by X may be the same as or different from each other. Furthermore, the multiple groups represented by X may be bonded to each other to form a ring.

[0210] m is a number that satisfies the valence of M and is determined by the valence of the transition metal atom M and the valence of X, and is a number that can neutralize these positive and negative valences. Here, when the absolute value of the valence of the transition metal atom M is a and the absolute value of the valence of X is b, the relationship a-2=B×n holds. More specifically, for example, when M is Ti 4+ and X is Cl - When , n is 2.

[0211] In the general formula (8), Y represents a neutral ligand having an electron-donating group, and n, which represents the number of Y, represents an integer from 0 to 3, preferably 1 or 2. An electron-donating group refers to a group having unpaired electrons that can be donated to a metal, and Y can be any group as long as it is a neutral ligand having electron-donating properties. Specific examples of the neutral ligand Y include:

[0212] For example, chain or cyclic saturated or unsaturated ethers such as diethyl ether, dimethyl ether, diisopropyl ether, tetrahydrofuran, furan, dimethyl furan, anisole, diphenyl ether, and methyl tert-butyl ether;

[0213] For example, acetaldehyde, propionaldehyde, n-butyraldehyde, benzaldehyde, p-nitrobenzaldehyde, p-methylbenzaldehyde, phenylacetaldehyde and other chain or cyclic saturated or unsaturated aldehydes;

[0214] For example, chain or cyclic saturated or unsaturated ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, acetophenone, benzophenone, n-butyl ketone, benzyl methyl ketone, etc.

[0215] For example, formamide, acetamide, benzamide, n-valeramide, stearamide, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylpropionamide, N,N-dimethyl-n-butylamide and other chain or cyclic saturated or unsaturated amides;

[0216] For example, acetic anhydride, succinic anhydride, maleic anhydride and other chain or cyclic saturated or unsaturated anhydrides;

[0217] For example, chain or cyclic saturated or unsaturated imides such as succinimide and phthalimide;

[0218] For example, chain or cyclic saturated or unsaturated esters such as methyl acetate, ethyl acetate, benzyl acetate, phenyl acetate, ethyl formate, ethyl propionate, ethyl stearate, and ethyl benzoate;

[0219] For example, trimethylamine, triethylamine, triphenylamine, dimethylamine, aniline, pyrrolidine, piperidine, morpholine and other chain or cyclic saturated or unsaturated amines;

[0220] For example, nitrogen-containing heterocyclic compounds such as pyridine, α-methylpyridine, β-methylpyridine, quinoline, isoquinoline, 2-methylpyridine, pyrrole, oxazole, imidazole, pyrazole, and indole;

[0221] For example, sulfur-containing heterocyclic compounds such as thiophene and thiazole;

[0222] For example, phosphines such as trimethylphosphine, triethylphosphine, tri-n-butylphosphine, and triphenylphosphine;

[0223] For example, saturated or unsaturated nitriles such as acetonitrile and benzonitrile;

[0224] For example, inorganic salts such as lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride; inorganic compounds such as carbon monoxide and carbon dioxide;

[0225] For example, the aforementioned organometallic compound (B) and the like.

[0226] In addition, these compounds may be partially substituted with substituents such as alkyl groups, halogen groups, nitro groups, carbonyl groups, amino groups, etc. As Y in the above formula (7), among these neutral ligands, ethers, aldehydes, ketones, nitrogen-containing heterocyclic compounds, and inorganic salts are preferred.

[0227] In the above general formula (8), i is an integer of 1 to 3, and preferably 2 or 3.

[0228] In the present invention, among the specific transition metal compounds that satisfy the above requirements, [hydrobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)]borate zirconium trichloride or [hydrotris(3-mesitylpyrazol-1-yl)]borate zirconium trichloride is particularly preferred.

[0229] Furthermore, the transition metal compound may form a complex such as a dimer, trimer, or oligomer via these neutral ligands, or may form a cross-linked structure such as a μ-oxygen bridge compound via these neutral ligands.

[0230] The aforementioned organometallic compound contained in the polymerization catalyst component is mainly used as a component (scavenger) to deactivate harmful impurities in the polymerization reaction system. Of course, it is also possible to function as an auxiliary catalyst for olefin polymerization. There is no particular limitation as long as it is a well-known organometallic compound that exhibits such performance. As such an organometallic compound, specifically, the above-mentioned (B) organometallic compound can be cited, and preferably, the above-mentioned general formula (1): AlR n X 3-n The aluminum-containing compound shown (for example, triisobutylaluminum) can be used. Of course, organometallic compounds such as organometallic oxide compounds used in known olefin polymerization catalysts can also be used.

[0231] When using above-mentioned catalyzer, can obtain the ethylene polymer particles of fine particle size, have the compound of polymerizable double bond according to employed alkene etc., can obtain the olefin polymer particles (for example ethylene polymer particles of functional group) containing functional group sometimes.In addition, by the ethylene polymer particles of fine particle size are carried out modification, also can obtain the ethylene polymer particles of functional group containing.

[0232] The particle diameter that obtains as mentioned above is little and may have the magnesium compound particle of the present invention of particle surface concavo-convex shape or the magnesium compound particle that alkoxyl group is more are used as the carrier of the solid catalyst component of polymerization catalyst, and the particle diameter of the polymer that obtains by implementing slurry polymerization, gas phase polymerization etc., i.e. ethylene polymer particles (particle α, particle α 1) is also little, and flowability is good. In addition, the ethylene polymer particles containing functional group that obtains by modifying the polymer that obtains is also little in particle diameter, and flowability is good. Particularly aforementioned ethylene polymer particles have concavo-convex shape on the surface, and therefore can expect that particle flowability is more excellent.

[0233] In addition, above-mentioned ethylene polymer particles can be made into the molded body that has used various molding methods.The feature of above-mentioned ethylene polymer particles and the ethylene polymer particles that contain functional group is that particle diameter is little, has spherical shape, therefore use the molded body that can directly utilize the molding method of this feature to obtain and become preferred example.Specifically, can by ethylene polymer particles being pressed into after being filled in the mold on one side, compression molding that compresses at the temperature below the melting point of polymer or aforementioned compression back so-called melt compression molding method etc., obtain the molded body with expected shape and function.In addition, according to the required performance of molded article, also can and use other resins, or further mix various additives and carry out molding.In addition, because particle diameter is little, even therefore the higher polymer of molecular weight also easily becomes molten state, therefore if be used for extrusion molding, injection molding etc. of high molecular weight polymer, then can expect to obtain few film, sheet, injection molded body such as fisheye.

[0234] Examples of molded products obtained by molding the ethylene polymer particles and / or functional group-containing ethylene polymer particles of the present invention include light diffusion films, electronic book substrates, lithium batteries, components for separators of lithium ion secondary batteries, components for optical filters, components for electronic paper, porous materials such as breathable films, and sintered filters.

[0235] In addition, the ethylene polymer particles and functional group-containing ethylene polymer particles of the present invention can be suitably used as ultraviolet absorbers, antioxidants, anti-blocking agents and raw materials for cosmetics (foundation), resin modifiers, lubricity imparting agents, colorants, matting agents for coatings, light diffusion additives, insulating fillers, crystal nucleating agents, chromatographic filling materials, carriers for immunodiagnostic drugs, spacers for forming gaps in liquid crystal substrates, and catalyst carriers.

[0236] And then, the particle diameter of ethylene-based polymer particles of the present invention and the ethylene-based polymer particles containing functional group is little, for having surface concavo-convex shape, therefore, can obtain aperture and be so-called pore size (pore size) little and have uniform aperture and be the sintered body as porous body of narrow pore size distribution, this sintered body can be preferably used as the filtration of filter, drinking water, fruit juice, fruit wine, wines etc. of the filtration of process water.In addition, owing to having surface concavo-convex shape, therefore from aspects such as surface-area being big, also can expect to give special filtering function.

[0237] Furthermore, by selecting the method and conditions for producing the magnesium compound particles, it is possible to produce olefin polymer particles (particles β) having a smooth surface, that is, to control the shape of the olefin polymer particles. The olefin polymer particles (β) can also be used as a raw material for the same applications as described above. In this case, it is expected that the performance of the aforementioned applications can be adjusted by adjusting the particle shape.

[0238] Furthermore, by using the functional group-containing ethylene polymer particles of the present invention to produce a sintered body, it is unnecessary to perform modification after the production of the sintered body, and a uniformly modified sintered body can be obtained.

[0239] Example

[0240] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

[0241] (Method for measuring average particle size of polymer particles)

[0242] Using a TM4000 scanning electron microscope manufactured by Hitachi High-Technologies Corporation, images of three random locations in a measurement sample weighing several grams were captured, and the particle size distribution was determined using image analysis software (MacView manufactured by Mountech) from the obtained SEM photographs.

[0243] (Polymerization activity (mileage))

[0244] The Mg content of the obtained polymer particles was measured using an ICPE-9820 ICP measuring apparatus manufactured by Shimadzu Corporation, and the polymerization activity based on Mg metal was calculated by a conventional method.

[0245] (Method for measuring the average particle size of Mg compound fine particles)

[0246] The average particle size of the polymer particles and the measured values ​​of the polymerization activity are used to calculate the average particle size by a conventional method.

[0247] (Measured by the mercury intrusion porosimeter described above)

[0248] Measurements were made using a mercury porosimeter (trade name: PoreMaster 60GT, manufactured by Quantachrome) using conventional methods. Pore volume values ​​were determined by analyzing the measurement data using analysis software (trade name: PoreMaster for Windows) included with the instrument and by accumulating the pore volume for pores with diameters of 0.1 to 1 μm.

[0249] (Electron microscope observation)

[0250] Electron micrographs are observed and photographed using, for example, a TM4000 Plus scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) by a conventional method at a magnification of 1000 times.

[0251] Based on the photograph, the proportion of particles having five or more protrusions on half the surface of the particle among particles observed in an arbitrary 100 μm square area was determined by visual inspection.

[0252] The protrusion has a width of 1 / 100 to 1 / 3 of the diameter of the particle.

[0253] (Intrinsic viscosity [η])

[0254] The intrinsic viscosity [η] is measured in accordance with ASTM D4020 by dissolving polymer particles in decalin at a temperature of 135°C.

[0255] [Example 1]

[0256] Preparation of component (A1)

[0257] 95.2 g (1.0 mol) of anhydrous magnesium chloride, 332 ml of decane, 260.5 g (2.0 mol) of 2-ethyl-1-hexanol, and 298.6 g (1.0 mol) of 2-octyl-1-dodecanol were mixed and reacted at 140° C. for 3 hours to obtain a uniform solution (component (A1)).

[0258] Preparation of magnesium compound particles (X-1)

[0259] A 1000 ml flask thoroughly purged with nitrogen was charged with 50 ml of component (A) (50 mmol in terms of magnesium atoms) and 400 ml of purified decane. Using CLEARMIX CLM-0.8S manufactured by Organo, 51.5 mmol of triethylaluminum (Al / Mg = 1.03 mmol) diluted with purified decane was added dropwise over 1 hour while maintaining the liquid temperature at 0°C. The mixture was then heated to 80°C over 5 hours and allowed to react for 1 hour. Subsequently, 92 mmol of triethylaluminum (total Al / Mg = 2.87 mmol) diluted with purified decane was added dropwise over 1 hour while maintaining the temperature at 80°C. The mixture was then heated and reacted for a further 1 hour. After the reaction was completed, the solid portion was collected by filtration, thoroughly washed with decane, and 100 ml of decane was added to prepare a decane slurry of magnesium compound particles (X-1). The average particle size of the obtained magnesium compound particles (X-1) was 0.86 μm.

[0260] Other results are shown in Table 1.

[0261] Synthesis of solid catalyst component using magnesium compound particles (X-1)

[0262] 68 mL of decane was added to a 200 mL glass reactor that had been purged with nitrogen, and 18 mL of the decane slurry of the magnesium compound particles (X-1) prepared above (3.8 mmol in terms of Mg atoms) was added under stirring. Subsequently, 10 mL of a decane slurry of a transition metal compound represented by the following formula (0.0021 mmol / mL in terms of Zr atoms) was added dropwise, and the mixture was reacted at 35°C for 4 hours. The reactant was then filtered and washed twice with 50 mL of decane. After filtration, 100 mL of decane was added to prepare a decane slurry of a solid catalyst component (1). A portion of the obtained slurry of the solid catalyst component (1) was collected and its concentration was investigated. The Zr concentration was 0.00020 mmol / mL. (94 mol% of the supplied transition metal compound was supported.)

[0263] [Chemistry 6]

[0264]

[0265] Polymerization of ethylene

[0266] A stainless steel autoclave with an internal volume of 1000 ml and thoroughly purged with nitrogen was charged with 500 ml of decane, and ethylene was passed through at room temperature at 100 liters / hour for 15 minutes to saturate the liquid phase and the gas phase. The temperature was then raised to 65° C., and while ethylene was passed through at 0.4 liters / hour, 1.25 ml of a decane solution of triisobutylaluminum (1.0 mmol / ml in terms of Al atoms) and 4.2 ml of a slurry of the solid catalyst component (1) (0.16 mmol in terms of Mg atoms, 0.00083 mmol in terms of Zr atoms) were added. The mixture was stirred for 5 minutes while maintaining the temperature, and then 90 mg of EMULGEN was added.

[0267] The autoclave was then sealed, 10 ml of hydrogen was added, and the temperature was raised to 70°C. Ethylene was then supplied at a rate of 1.0 liter / hour. After the pressure reached 0.35 MPaG, ethylene was continued to be supplied at 0.35 MPaG. When the ethylene supply reached 56 liters after the temperature was raised to 70°C, the ethylene supply was stopped, the autoclave was cooled, and the ethylene pressure was released (ethylene supply time: 147 minutes). The resulting polymer slurry was filtered, washed with hexane, and dried under reduced pressure at 80°C for 10 hours to obtain 62 g of a polymer. The resulting polymer had an uneven surface.

[0268] [Examples 2 to 4]

[0269] Hereinafter, magnesium compound particles were produced in the same manner as in Example 1 except that the conditions were set as shown in Table 1, and a polymer was obtained using the produced magnesium compound particles.

[0270] In Examples 2 to 4, the obtained polymers had a surface with irregularities.

[0271] [Table 1]

[0272]

[0273] The above results show that olefin polymer particles obtained by an olefin polymerization catalyst containing magnesium compound particles produced under the conditions satisfying the requirement of [1] of the above-mentioned [Solution to the Problems] have a shape with many surface irregularities.

[0274] The following Examples 11 and thereafter, together with Examples 1 to 4, correspond to Examples [6] of the aforementioned [Means for Solving the Problems] and are examples for illustrating the control of the shape of olefin polymer particles by controlling the Al / Mg ratio of the magnesium compound particles, and for producing olefin polymer particles having a smooth surface using an olefin polymerization catalyst mainly containing magnesium compound particles having a specific Al / Mg ratio.

[0275] [Example 11]

[0276] Preparation of component (A1)

[0277] 95.2 g (1.0 mol) of anhydrous magnesium chloride, 332 ml of decane, 260.5 g (2.0 mol) of 2-ethyl-1-hexanol, and 298.6 g (1.0 mol) of 2-octyl-1-dodecanol were mixed and reacted at 140° C. for 3 hours to obtain a uniform solution (component (A11)).

[0278] Preparation of magnesium compound particles (X-11)

[0279] A 1000 ml flask thoroughly purged with nitrogen was charged with 50 ml of component (A) (50 mmol in terms of magnesium atoms) and 400 ml of purified decane. Using CLEARMIX CLM-0.8S manufactured by Organo, 56 mmol of triethylaluminum (Al / Mg = 1.12 mmol) diluted with purified decane was added dropwise over 1 hour while maintaining the liquid temperature at 0°C. The mixture was then heated to 80°C over 5 hours and allowed to react for 1 hour. Subsequently, 92.5 mmol of triethylaluminum (total Al / Mg = 2.97 mmol) diluted with purified decane was added dropwise over 1 hour while maintaining the temperature at 80°C. The mixture was then heated and reacted for a further 1 hour. After the reaction was completed, the solid portion was collected by filtration, thoroughly washed with decane, and 100 ml of decane was added to prepare a decane slurry of magnesium compound particles (X-1). The average particle size of the obtained magnesium compound particles (X-1) was 0.74 μm.

[0280] Other results are shown in Table 2.

[0281] Synthesis of solid catalyst component using magnesium compound particles (X-11)

[0282] 68 mL of decane was added to a 200 mL glass reactor that had been purged with nitrogen, and 22 mL of the decane slurry of the magnesium compound particles (X-1) prepared above (4.9 mmol in terms of Mg atoms) was added under stirring. Subsequently, 10 mL of a decane slurry of a transition metal compound represented by the following formula (0.0027 mmol / mL in terms of Zr atoms) was added dropwise, and the mixture was reacted at 35°C for 4 hours. The reactant was then filtered and washed twice with 50 mL of decane. After filtration, 100 mL of decane was added to prepare a decane slurry of the solid catalyst component (1). A portion of the obtained slurry of the solid catalyst component (11) was collected and its concentration was investigated. The Zr concentration was 0.00027 mmol / mL. (100 mol% of the supplied transition metal compound was supported.)

[0283] [Chemistry 7]

[0284]

[0285] Polymerization of ethylene

[0286] A stainless steel autoclave with an internal volume of 1000 ml and thoroughly purged with nitrogen was charged with 500 ml of decane, and ethylene was allowed to flow at 100 liters / hour for 15 minutes at room temperature to saturate the liquid phase and the gas phase. The temperature was then raised to 65° C., and while ethylene was flowing at 0.4 liters / hour, 1.25 ml of a decane solution of triisobutylaluminum (1.0 mmol / ml in terms of Al atoms) and 3.3 ml of a slurry of the solid catalyst component (11) (0.16 mmol in terms of Mg atoms, 0.00090 mmol in terms of Zr atoms) were added. The mixture was stirred for 5 minutes while maintaining the temperature, and then 90 mg of EMULGEN was added.

[0287] The autoclave was then sealed, 10 ml of hydrogen was added, and the temperature was raised to 70°C. Ethylene was then supplied at a rate of 1.0 liter / hour. After the pressure reached 0.35 MPaG, ethylene was continued to be supplied at 0.35 MPaG. When the ethylene supply reached 56 liters after the temperature was raised to 70°C, the ethylene supply was stopped, the autoclave was cooled, and the ethylene pressure was released (ethylene supply time: 135 minutes). The resulting polymer slurry was filtered, washed with hexane, and dried under reduced pressure at 80°C for 10 hours to yield 61 g of a polymer. The resulting polymer had a smooth surface and a nearly spherical shape.

[0288] [Examples 12 to 17]

[0289] Magnesium compound particles were produced in the same manner as in Example 11, except that the conditions shown in Table 2 were used, and polymers were obtained using the particles. The results are shown in Table 2. In Examples 12 to 17, the polymers obtained also had smooth surfaces and nearly spherical shapes. The results are summarized in Table 2.

[0290] [Table 2]

[0291]

[0292] From the results in Tables 1 and 2, it is understood that olefin polymer particles having a desired particle shape can be produced by controlling the Al / Mg molar ratio to a specific value.

[0293] (Shape of olefin polymer particles: Experimental example corresponding to [7] of [Means for solving the problem])

[0294] [Examples 21-22]

[0295] The olefin polymer particles of Examples 1 and 3 were measured for pore volumes within the pore diameter range of 0.1 to 1 μm using the mercury porosimeter described above. The proportion of particles with protrusions was also visually determined based on electron micrographs of the particles. The results are summarized in Table 3.

[0296] [Comparative Examples 21-22]

[0297] The olefin polymer particles of Examples 13 and 16 were measured for pore volumes within the pore diameter range of 0.1 to 1 μm using the mercury porosimeter described above. The proportion of particles having protrusions was also visually determined based on electron micrographs of the particles. The results are summarized in Table 3.

[0298] [Table 3]

[0299] Average particle size / μm [η] / (dl / g) <![CDATA[Pore volume / (mm 3 / g)]]> Ratio of particles with protrusions / % Example 21 14.7 15.7 45 ≥50 Example 22 12.7 14.5 32 ≥50 Comparative Example 21 12.1 13.5 21 ≤20 Comparative Example 22 12.2 14.9 13 ≤20

Claims

1. A method for producing magnesium compound particles, comprising a contacting step of bringing a magnesium compound-containing solution (A) into contact with an organometallic compound (B) at a temperature within a range of -20°C to 10°C. The magnesium compound-containing solution (A) comprises: (A-1) a magnesium-containing compound, and (A-2) a compound containing an element selected from Group 15 and Group 16 elements of the periodic table; The organometallic compound (B) comprises: a metal element (MB) selected from the first, second and thirteenth groups of the periodic table, wherein: Does not include magnesium; Furthermore, the magnesium compound particles satisfy the following requirements (i) and (ii): (i) Particle size is 0.05 to 0.90 μm, (ii) The ratio of the molar content of magnesium atoms [Mg] to the molar content of atoms of the metal element (MB) [MB], that is, [Mg] / [MB], is 1.0 or more and 11.5 or less.

2. The manufacturing method according to claim 1, wherein The ratio of the molar amount [MBr] of the metal element (MB) atoms used in the contact step to the molar amount [Mgr] of magnesium atoms contained in the magnesium compound-containing solution (A), that is, [MBr] / [Mgr], is 2.5 to 2.

96.

3. The manufacturing method according to claim 1, wherein In the contacting step, the magnesium compound-containing solution (A) and the organometallic compound (B) are brought into contact for 0.6 to 10 hours.

4. The manufacturing method according to claim 1, wherein The [Mg] / [MB] is 5.0 to 11.

3.

5. The manufacturing method according to claim 1, wherein The magnesium compound-containing solution (A) further contains (A-3) a liquid hydrocarbon compound.

6. A method for controlling the shape of olefin polymer particles, comprising: a contacting step of bringing a magnesium-containing compound solution (A) into contact with an organometallic compound (B) at a temperature range of -20°C to 10°C, wherein the magnesium-containing compound solution (A) comprises (A-1) a magnesium-containing compound and (A-2) a compound comprising an element selected from Groups 15 and 16 of the periodic table, and the organometallic compound (B) comprises a metal element (MB) selected from Groups 1, 2, and 13 of the periodic table, excluding magnesium, and a step of polymerizing olefins in the presence of an olefin polymerization catalyst comprising magnesium compound particles having a particle size of 0.05 to 0.90 μm produced in the contact step and a transition metal compound component to produce olefin polymer particles; The ratio of the molar content [Mg] of magnesium atoms in the magnesium compound particles to the molar content [MB] of the metal element (MB) atoms, ie, [Mg] / [MB], is controlled within a range of 1.0 to 20.

7. Olefin polymer particles having an average particle size of 3 to 25 μm, The intrinsic viscosity η in decalin at 135°C is 5 to 50 dl / g, The pore volume of the pores with a diameter of 0.1 to 1 μm determined by mercury porosimetry is 25 to 100 mm 3 / g.

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