3-methyl-1-butene-based polymer particle, and production method of the same

Abstract

To provide a 3-methyl-1-butene-based polymer particle having a predetermined particle size and a narrow particle size distribution, and a method of the same.SOLUTION: A 3-methyl-1-butene-based polymer particle has a particle size (Dv50) of a cumulative volume of 50% of 30-200 μm, and a ratio (Dv50 / Dn50) of a particle size (Dv50) of a cumulative volume of 50% and a particle size (Dn50) of a cumulative number of 50% of 2.00 or less. A production method of a 3-methyl-1-butene-based polymer particle includes a process of performing coordination polymerization using a solid catalyst carrying a compound having a periodic table-group four transition metal atom, and satisfying the following formula (1). 20≤Dv'50×Y^(1 / 3)≤150 (1). In the formula (1), Dv'50 is a particle size (μm) of a cumulative volume of 50% of the solid catalyst, and Y is a catalytic activity value (Y) which is a value obtained by dividing a produced 3-methyl-1-butene-based polymer particle amount (g) by the solid catalyst amount (g) used when producing.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to 3-methyl-1-butene polymer particles and a method for producing the same. [Background technology]

[0002] 3-Methyl-1-butene polymers have excellent electrical properties, thermal properties, and chemical resistance, and it is expected that these properties will be utilized in a variety of fields.

[0003] For example, Patent Document 1 describes that high molecular weight 3-methylbutene-1 polymers and graft-modified polymers thereof are effective as powder coating materials. Furthermore, Patent Document 2 describes a selective sintering additive manufacturing method and a powder used therein, and describes a homopolymer and a copolymer of 3-methyl-1-butene as an example of a polyolefin contained in the powder. Furthermore, Patent Document 3 describes a laser-sinterable powder and a molded body formed from the laser-sinterable powder, and describes 3-methyl-1-butene as an example of an olefin that is a constituent monomer unit of the polyolefin resin contained in the laser-sinterable powder. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 60-206805 [Patent Document 2] Special Publication No. 2018-531163 [Patent Document 3] JP 2009-40870 A Summary of the Invention [Problem to be solved by the invention]

[0005] As described in Patent Documents 1 to 3, by microparticulating 3-methyl-1-butene polymers, it is being considered to develop them into powder coating materials and materials in the field of shaping by powder sintering, such as materials for forming molded bodies produced by the SLS method of 3D printers. However, in Patent Document 1, the powder (particle) formed from the high molecular weight 3-methylbutene-1 polymer and the graft modified polymer thereof is described only as a relatively coarse powder, and there is no description of a small particle size powder. Moreover, in Patent Documents 2 and 3, no specific investigation is made into the use of 3-methyl-1-butene polymers.

[0006] In general, when particles are too small, aggregation between particles is likely to occur. Particles with excessively large particle size due to aggregation between particles, or particles manufactured as coarse powder, tend to have poor appearance when used for powder coating applications. In addition, when such particles are used for SLS applications in 3D printers, the appearance tends to be poor, and it becomes difficult to obtain a molded body having the desired dimensions. Therefore, it is desirable for particles used for powder coating applications and SLS applications in 3D printers to have an appropriate particle size. Furthermore, particles having a wide particle size distribution have the same problems as those mentioned above, and it is therefore desirable to have particles having a narrow particle size distribution.

[0007] Therefore, an object of the present invention is to provide 3-methyl-1-butene polymer particles having a predetermined particle size and a narrow particle size distribution, and a method for producing the same.

[0008] As a result of intensive research aimed at solving the above problems, the present inventors have conceived the following invention and found that the problems can be solved. That is, the present invention is as follows. [1] 3-methyl-1-butene polymer particles having a particle diameter at 50% cumulative volume (Dv50) of 30 to 200 μm, and a ratio (Dv50 / Dn50) of the particle diameter at 50% cumulative volume (Dv50) to the particle diameter at 50% cumulative number (Dn50) of 2.00 or less. [2] The 3-methyl-1-butene polymer particles according to the above [1], which have a melting point Tm of 265.0 to 290.0° C. as measured at a heating rate of 10° C. / min in differential scanning calorimetry. [3] The 3-methyl-1-butene polymer particles according to the above [1] or [2], which are produced by a production method having a step of carrying out coordination polymerization. [4] The 3-methyl-1-butene polymer particles according to the above [3], wherein the coordination polymerization is carried out using a solid catalyst supporting a compound having a transition metal atom of Group 4 of the periodic table. [5] The 3-methyl-1-butene polymer particles according to the above item [4], in which a particle size (Dv'50 [μm]) at 50% cumulative volume of the solid catalyst and a catalytic activity value (Y) obtained by dividing the amount (g) of the 3-methyl-1-butene polymer particles produced by the production method by the amount (g) of the solid catalyst used in the production satisfy the following formula (1): 20≦Dv'50×Y^(1 / 3)≦150 (1) [6] The 3-methyl-1-butene polymer particles according to the above [4] or [5], wherein the particle diameter at 50% cumulative volume of the solid catalyst (Dv'50) is 2.5 to 30 µm. [7] The 3-methyl-1-butene polymer particles according to the above [5] or [6], wherein the catalytic activity value (Y) is 100 or more. [8] The 3-methyl-1-butene polymer particles according to any one of [4] to [7] above, wherein the coordination polymerization is carried out by adding the solid catalyst so that the amount of the metal atom is 0.00150 to 0.01000 parts by mass relative to 100 parts by mass of the 3-methyl-1-butene. [9] A method for producing 3-methyl-1-butene polymer particles, comprising the steps of supporting a compound having a transition metal atom of Group 4 of the periodic table and carrying out coordination polymerization using a solid catalyst that satisfies the following formula (1): 20≦Dv'50×Y^(1 / 3)≦150 (1) (In formula (1), Dv'50 is the particle size (μm) of the solid catalyst at 50% cumulative volume, and Y is the catalyst activity value (Y) obtained by dividing the amount (g) of the produced 3-methyl-1-butene polymer particles by the amount (g) of the solid catalyst used in the production.)

[10] The method for producing 3-methyl-1-butene polymer particles according to the above [9], wherein the particle diameter at 50% cumulative volume of the solid catalyst (Dv'50) is 2.5 to 30 µm. Effect of the Invention

[0009] According to the present invention, it is possible to provide 3-methyl-1-butene polymer particles having a predetermined particle size and a narrow particle size distribution, and a method for producing the same. The 3-methyl-1-butene polymer particles of the present invention are suitable as a powder coating material or a material for forming a molded body produced by the SLS method of a 3D printer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the present invention will be described based on an example of an embodiment. However, the embodiment shown below is an example for embodying the technical idea of ​​the present invention, and the present invention is not limited to the following description. In addition, in this specification, preferred embodiments are shown, but a combination of two or more of the individual preferred embodiments is also a preferred embodiment. When there are several numerical ranges for matters shown as numerical ranges, the lower limit and upper limit can be selectively combined to form a preferred embodiment. In this specification, when a numerical range is stated as "XX to YY", it means "not less than XX and not more than YY".

[0011] <3-Methyl-1-butene polymer particles> The 3-methyl-1-butene polymer particles (hereinafter also referred to as polymer particles) of this embodiment are characterized in that the particle diameter at 50% cumulative volume (Dv50) is 30 to 200 μm, and the ratio (Dv50 / Dn50) of the particle diameter at 50% cumulative volume (hereinafter also referred to as Dv50) to the particle diameter at 50% cumulative number (hereinafter also referred to as Dn50) is 2.00 or less. In this specification, the particle size at 50% cumulative volume (Dv50) means the particle size at which the cumulative volume is 50% as measured in accordance with JIS Z 8827-1:2008, and specifically, it can be measured by the method described in the examples. In this specification, the particle size at 50% cumulative number (Dn50) means the particle size at which the cumulative number is 50%, as measured in accordance with JIS Z 8827-1:2008, and specifically, it can be measured by the method described in the examples. Furthermore, the ratio of Dv50 to Dn50 (Dv50 / Dn50) is an index of particle size distribution, and the larger this ratio is, the broader the particle size distribution is.

[0012] The particle diameter at 50% cumulative volume (Dv50) of the 3-methyl-1-butene polymer particles of this embodiment is 30 to 200 μm. When the Dv50 of the 3-methyl-1-butene polymer particles is within the above range, the aggregation of the particles can be suppressed, and when used for powder coating, a coating film having a good appearance can be obtained, and when used for SLS method of 3D printer, a molded body having a good appearance and desired dimensions can be obtained. In addition, the productivity is also good. From the viewpoint of suppressing particle aggregation and obtaining 3-methyl-1-butene polymer particles more suitable for powder coating applications and SLS applications of 3D printers, and from the viewpoint of productivity, the Dv50 of the 3-methyl-1-butene polymer particles is preferably 35 to 190 μm, more preferably 40 to 185 μm, and even more preferably 43 to 180 μm. In addition, by controlling the particle size at 50% of the cumulative volume of the solid catalyst used in polymerizing 3-methyl-1-butene (hereinafter also referred to as Dv'50) and the catalyst activity value (Y) described below, 3-methyl-1-butene polymer particles having a predetermined particle size can be obtained.

[0013] The ratio (Dv50 / Dn50) of the particle diameter at 50% cumulative volume (Dv50) to the particle diameter at 50% cumulative number (Dn50) of the 3-methyl-1-butene polymer particles of this embodiment is 2.0 or less. When the Dv50 / Dn50 of the 3-methyl-1-butene polymer particles is within the above range, a coating film having a good appearance can be obtained when used for powder coating applications, and a molded body having a good appearance and desired dimensions can be obtained when used for SLS applications of 3D printers. From the viewpoint of obtaining 3-methyl-1-butene polymer particles more suitable for powder coating applications and SLS applications of 3D printers, the molecular weight is preferably 1.8 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. In addition, by carrying out the coordination polymerization using a solid catalyst carrying a compound having a transition metal atom of Group 4 of the periodic table, which will be described later, to produce polymer particles, it is possible to obtain 3-methyl-1-butene polymer particles having a narrow particle size distribution.

[0014] The melting point Tm measured at a heating rate of 10 ° C. / min in differential scanning calorimetry of the 3-methyl-1-butene polymer particles of this embodiment is preferably 265.0 ° C. or more, more preferably 270.0 ° C. or more, and even more preferably 275.0 ° C. or more from the viewpoint of improving the heat resistance of a coating film or a molded body using the 3-methyl-1-butene polymer particles (for example, a coating film formed by powder coating, or a molded body manufactured by the SLS method of a 3D printer, etc.), and is preferably 290.0 ° C. or less, more preferably 289.0 ° C. or less, and even more preferably 288.0 ° C. or less from the viewpoint of thermal stability during molding. That is, the melting point Tm of the 3-methyl-1-butene polymer particles is preferably 265.0 to 290.0 ° C., more preferably 270.0 to 289.0 ° C., and even more preferably 275.0 to 288.0. In addition, 3-methyl-1-butene polymer particles having a desired melting point can be obtained by using an α-olefin or the like described below as a comonomer, adjusting the type and content of the α-olefin, and copolymerizing it with 3-methyl-1-butene to produce polymer particles. The melting point Tm measured at a heating rate of 10°C / min in differential scanning calorimetry of 3-methyl-1-butene polymer particles means the peak temperature measured by using a differential scanning calorimeter to raise the temperature of a test piece from 30°C to 320°C at 10°C / min under a nitrogen flow rate (100 mL / min), hold the test piece at 320°C for 5 minutes, lower the temperature to -70°C at 10°C / min, hold the test piece at -70°C for 5 minutes, and then raise the temperature to 320°C at 10°C / min. Specifically, the melting point Tm can be measured by the method described in the Examples.

[0015] [3-Methyl-1-butene polymer] The 3-methyl-1-butene polymer may be a 3-methyl-1-butene homopolymer or a copolymer of 3-methyl-1-butene and an unsaturated hydrocarbon. The unsaturated hydrocarbon may be, for example, an α-olefin, and from the viewpoint of good copolymerizability, preferably an α-olefin having 2 to 20 carbon atoms. From the viewpoint of favorably exerting the mechanical properties (adequate strength, flexibility, and impact resistance) of the coating film or molded article, the 3-methyl-1-butene polymer is preferably at least one selected from the group consisting of a 3-methyl-1-butene homopolymer and a copolymer of 3-methyl-1-butene and an α-olefin having 2 to 20 carbon atoms, and more preferably a copolymer of 3-methyl-1-butene and an α-olefin having 2 to 20 carbon atoms. The copolymer may be a random copolymer, a block copolymer, or an alternating copolymer. The method for producing the copolymer is not limited as long as it does not impair the effects of the present invention, and any known copolymerization method can be used.

[0016] When the 3-methyl-1-butene polymer is the above-mentioned copolymer, the content of structural units derived from an α-olefin in the copolymer is preferably more than 0 mol % and 20 mol % or less. From the viewpoint of flexibility and impact resistance of the coating film or molded article, the content of structural units derived from α-olefin in the copolymer is more preferably 0.1 mol % or more, and even more preferably 0.5 mol % or more. From the viewpoint of the heat resistance of the coating film or the molded product, the content of structural units derived from α-olefin is more preferably 15 mol % or less, and even more preferably 10 mol % or less. The content of the structural unit derived from an α-olefin in the copolymer can be determined by a Fourier transform infrared spectrophotometer (FT-IR).

[0017] When the 3-methyl-1-butene polymer is the above-mentioned copolymer, the content of structural units derived from 3-methyl-1-butene in the copolymer is preferably 80 mol % or more and less than 100 mol %. From the viewpoint of heat resistance of the coating film or molded article, the content of structural units derived from 3-methyl-1-butene in the copolymer is more preferably 85 mol% or more, and even more preferably 90 mol% or more, and from the viewpoint of flexibility and impact resistance of the coating film or molded article, the content of structural units derived from 3-methyl-1-butene in the copolymer is more preferably 99.9 mol% or less, and even more preferably 99.5 mol% or less. That is, the content of structural units derived from 3-methyl-1-butene in the copolymer is more preferably 85 to 99.9 mol%, and even more preferably 90 to 99.5 mol%.

[0018] From the viewpoint of more suitably exerting the physical properties of the 3-methyl-1-butene polymer, the α-olefin having 2 to 20 carbon atoms is preferably an α-olefin having 4 to 16 carbon atoms, and more preferably an α-olefin having 4 to 12 carbon atoms. In addition, the α-olefin having 2 to 20 carbon atoms may be linear or branched.

[0019] Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexene, and vinylnorbornane. The α-olefins having 2 to 20 carbon atoms may be used alone or in combination of two or more kinds.

[0020] The melting point Tm of the 3-methyl-1-butene polymer of this embodiment is the same as the melting point of the 3-methyl-1-butene polymer particles. The melting point Tm of the 3-methyl-1-butene polymer means a peak temperature measured by a method similar to the method for measuring the melting point Tm of the 3-methyl-1-butene polymer particles, and specifically, the melting point Tm can be measured by the method for measuring the melting point Tm of the 3-methyl-1-butene polymer particles described in the Examples.

[0021] The content of the 3-methyl-1-butene polymer in the 3-methyl-1-butene polymer particles is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and may be 100% by mass.

[0022] The 3-methyl-1-butene polymer particles of the present invention are preferably produced by a production method having a step of performing coordination polymerization described later, and more preferably produced by the <Production method for 3-methyl-1-butene polymer particles> described later.

[0023] <Method of producing 3-methyl-1-butene polymer particles> The method for producing 3-methyl-1-butene polymer particles of this embodiment includes a step of supporting a compound having a transition metal atom of Group 4 of the periodic table and carrying out coordination polymerization using a solid catalyst that satisfies the following formula (1). 20≦Dv'50×Y^(1 / 3)≦150 (1) In formula (1), Dv'50 is the particle size (μm) of 50% cumulative volume of the solid catalyst, and Y is the catalytic activity value (Y) obtained by dividing the amount (g) of the produced 3-methyl-1-butene polymer particles by the amount (g) of the solid catalyst used in the production.

[0024] [Solid catalyst] The polymerization reaction of 3-methyl-1-butene in the step of carrying out coordination polymerization uses a solid catalyst carrying a compound having a transition metal atom of Group 4 of the periodic table. The polymerization reaction of 3-methyl-1-butene is preferably carried out in the presence of a well-known solid catalyst such as a supported metallocene catalyst or a Ziegler-Natta catalyst. Specific examples of the transition metal atom of Group 4 of the periodic table used in the solid catalyst include titanium, zirconium, and hafnium, with titanium being preferred.

[0025] A solid catalyst (also called a supported catalyst) carrying a compound having a transition metal atom of Group 4 of the periodic table is preferably supplied to the polymerization reaction system in a state suspended in an inert organic solvent (preferably a saturated aliphatic hydrocarbon).

[0026] A preferred example of the supported catalyst is a magnesium-supported titanium catalyst in which the compound having a transition metal atom of Group 4 of the periodic table is titanium chloride and the support is magnesium chloride, which is a so-called Ziegler-Natta catalyst, or a supported metallocene catalyst in which a metallocene catalyst is supported on magnesium chloride, silica, or the like. From the viewpoints of ease of handling, availability, catalyst cost, and the like, a Ziegler-Natta catalyst is more preferred. Specifically, it is a magnesium-supported titanium catalyst obtained by contacting a magnesium compound suspended in an inert hydrocarbon solvent, a liquid titanium compound, and an electron donor compound having an ester bond or ether bond as necessary. The magnesium-supported titanium catalyst has a titanium atom, a magnesium atom, a halogen atom, and a plurality of ester bonds or ether bonds.

[0027] Examples of the inert hydrocarbon solvent used in the production of the magnesium-supported titanium catalyst include hexane, decane, and dodecane. Examples of the magnesium compound include anhydrous magnesium chloride, diethoxy magnesium, and methoxy magnesium chloride. Examples of the electron donor compound having an ester bond via a plurality of atoms include alkyl benzoate (the alkyl group preferably has 1 to 8 carbon atoms), alkyl p-toluate (the alkyl group preferably has 1 to 8 carbon atoms), alkyl pivalate (the alkyl group preferably has 1 to 8 carbon atoms), dialkyl phthalate (the alkyl group preferably has 1 to 8 carbon atoms), dialkyl malonate (the alkyl group preferably has 1 to 8 carbon atoms), and dialkyl succinate (the alkyl group preferably has 1 to 8 carbon atoms). Examples of the electron donor compound having an ether bond via a plurality of atoms include 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and 2-isopentyl-2-isopropyl-1,3-dimethoxypropane.

[0028] The atomic ratio of halogen atoms and titanium atoms (halogen atoms / titanium atoms) in the magnesium-supported titanium catalyst is usually 2 to 100, and preferably 4 to 90. The molar ratio of an electron donor compound having an ester bond or an ether bond to titanium atoms (electron donor compound / titanium atoms) in the magnesium-supported titanium catalyst is usually 0.01 to 100, and preferably 0.2 to 10. The atomic ratio of magnesium atoms and titanium atoms (magnesium atoms / titanium atoms) in the magnesium-supported titanium catalyst is usually 2 to 100, and preferably 4 to 50.

[0029] When the polymerization reaction of 3-methyl-1-butene is carried out by a liquid phase polymerization method, the magnesium supported titanium catalyst is preferably used in an amount of usually 0.001 to 2 mmol, preferably 0.005 to 1 mmol, calculated as titanium atom per 1 L of the total liquid volume.

[0030] The particle size at 50% cumulative volume of the solid catalyst (hereinafter also referred to as Dv'50) is preferably 2.5 to 30 μm, more preferably 4 to 28 μm, and further preferably 5 to 27 μm. When the Dv'50 of the solid catalyst is within the above range, 3-methyl-1-butene polymer particles having a predetermined particle size and a narrow particle size distribution can be easily obtained without a further microparticulation step after the polymerization reaction of 3-methyl-1-butene. The reason why it is easier to obtain 3-methyl-1-butene polymer particles having a predetermined particle size and a narrow particle size distribution by setting the particle size at 50% of the cumulative volume of the solid catalyst within the above range is unclear, but is thought to be as follows. When 3-methyl-1-butene is polymerized using a solid catalyst, the polymer grows in such a way that it covers the periphery of the solid catalyst. Therefore, 3-methyl-1-butene polymer particles according to the particle size of the solid catalyst are obtained. Therefore, it is considered that by setting the particle size at 50% of the cumulative volume of the solid catalyst within the above range, it is easy to obtain 3-methyl-1-butene polymer particles having a predetermined particle size. In addition, the ratio (Dv'50 / Dn'50) of the particle size at 50% cumulative volume (Dv'50) to the particle size at 50% cumulative number (Dn'50) of the solid catalyst supporting a compound having a transition metal atom of Group 4 of the periodic table is usually 2.0 or less, and the particle size distribution is narrow. This is thought to make it easier to obtain 3-methyl-1-butene polymer particles with a narrow particle size distribution.

[0031] When carrying out coordination polymerization, it is preferable to add the metal atom amount to 0.00150 to 0.01000 parts by mass, more preferably 0.00175 to 0.00800 parts by mass, and even more preferably 0.00200 to 0.00750 parts by mass, relative to 100 parts by mass of 3-methyl-1-butene. When the metal atom amount is 0.00150 parts by mass or more, good productivity is achieved. In addition, when the metal atom amount is 0.01000 parts by mass or less, it is possible to suppress the deterioration of the processability of coating films, molded bodies, etc., due to the metal residue remaining in the 3-methyl-1-butene polymer particles.

[0032] The catalytic activity value (Y), which is the value obtained by dividing the amount (g) of the 3-methyl-1-butene polymer particles produced by the production method of this embodiment by the amount (g) of the solid catalyst used in the production, is preferably 100 or more. Within the above range, 3-methyl-1-butene polymer particles having a predetermined particle size and a narrow particle size distribution can be easily and economically obtained. The catalytic activity value (Y) is more preferably 150 or more, and even more preferably 200 or more.

[0033] In the present embodiment, the cumulative volume 50% (Dv50) of the 3-methyl-1-butene polymer particles can be controlled by the particle size (Dv'50) at 50% cumulative volume of the solid catalyst supporting a compound having a transition metal atom of Group 4 of the periodic table and the catalytic activity value (Y), and the catalytic activity value (Y) satisfies the following formula (1). 20≦Dv'50×Y^(1 / 3)≦150 (1) When the catalyst activity value (Y) satisfies the above formula (1), 3-methyl-1-butene polymer particles having a predetermined particle size can be obtained. From the viewpoint of obtaining 3-methyl-1-butene polymer particles having a more specific particle size, the product of Dv'50 and Y^(1 / 3) is more preferably 25 or more and 138 or less, even more preferably 29 or more and 135 or less, and even more preferably 31 or more and 131 or less.

[0034] As a solid catalyst carrying a compound having a transition metal atom of Group 4 of the periodic table, for example, a solid titanium trichloride catalyst described in JP-A-54-107989 etc.; a magnesium-supported titanium catalyst described in JP-A-57-63310, JP-A-58-83006, JP-A-3-706, JP-P3476793, JP-P4-218508, JP-P2003-105022 etc.; a carrier-supported metallocene catalyst described in JP-A-2009-144148 or JP-A-2022-37931; and the like are suitably used.

[0035] The solid catalyst may be one produced by referring to the above-mentioned known literature, or may be a commercially available product. Commercially available solid titanium trichloride catalysts include, for example, "Solvay Catalyst CATA-1" manufactured by Tosoh Finechem Co., Ltd. Commercially available magnesium-supported titanium catalysts include, for example, "THC Series" manufactured by Toho Titanium Co., Ltd. and "PolyMax Series" manufactured by Clariant.

[0036] [Cocatalyst component] In the polymerization reaction of 3-methyl-1-butene, it is preferable to use a cocatalyst. The cocatalyst component used in the polymerization reaction of 3-methyl-1-butene is preferably an organometallic compound catalyst component, specifically an organoaluminum compound or a hydrolyzed polymer thereof. The organoaluminum compound is, for example, R a n AIX 3-n As shown in the figure.

[0037] R a n AIX 3-n R in a is preferably a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group, or an aryl group. Specific examples of the hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a tolyl group. R a n AIX 3-n In the above formula, X is preferably a halogen atom or a hydrogen atom, and n is preferably an integer of 1 to 3.

[0038] R a n AIX 3-nSpecific examples of the organoaluminum compound represented by the formula (I) include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and dimethylaluminum bromide; alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, and ethylaluminum dibromide; and alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride. Of the above specific examples, trialkylaluminum such as triethylaluminum and triisobutylaluminum are preferred.

[0039] For example, when the solid catalyst containing a compound having a transition metal atom of Group 4 of the periodic table is a magnesium-supported titanium catalyst component, the amount of the cocatalyst component added may be such that usually 0.1 to 10,000 g, preferably 1 to 5,000 g, of polymer is produced per gram of the magnesium-supported titanium catalyst component, and the amount is usually 0.1 to 1,000 mol, preferably about 0.5 to 500 mol, more preferably 1 to 200 mol per mol of titanium atom in the magnesium-supported titanium catalyst component.

[0040] [Polymerization reaction] The polymerization reaction of 3-methyl-1-butene can be carried out by a liquid phase polymerization method such as solution polymerization, suspension polymerization (slurry polymerization), bulk polymerization, or a gas phase polymerization method, or by other known polymerization methods. The polymerization reaction is preferably a suspension polymerization method.

[0041] [solvent] When the polymerization reaction of 3-methyl-1-butene is carried out by a liquid phase polymerization method, a solvent may not be used, or an inert hydrocarbon may be used as the solvent. Examples of the inert hydrocarbon solvent include saturated hydrocarbons such as pentane, cyclopentane, hexane, cyclohexane, heptane, isoheptane, and isooctane; aromatic hydrocarbons such as benzene and toluene; and the like. The solvent may be used alone or in combination of two or more kinds.

[0042] [Polymerization conditions] (Polymerization method) The polymerization reaction of 3-methyl-1-butene can be carried out by any of batch, semi-continuous and continuous methods. The polymerization reaction can also be carried out in two or more stages by changing the reaction conditions. (Polymerization temperature) The polymerization temperature in the polymerization reaction of 3-methyl-1-butene is usually 10 to 150° C., and preferably 30 to 120° C. If the polymerization temperature is within the above range, the progress of the polymerization reaction can be promoted while maintaining good catalytic activity, and the productivity becomes good. (Polymerization pressure) The polymerization pressure in the polymerization reaction of 3-methyl-1-butene is usually from normal pressure to 5 MPaG, preferably from 0.05 to 4 MPaG. If the polymerization pressure is within the above range, devices such as a high pressure-resistant reactor or an exhaust pump are not required, which is economically advantageous. (Polymerization time) The polymerization time in the polymerization reaction of 3-methyl-1-butene is usually 0.1 to 10 hours, preferably 0.5 to 7 hours. When the polymerization time is within the above range, the deterioration of the physical properties of the polymer caused by thermal degradation is suppressed, and polymer particles with good physical properties can be easily produced. (Stopping of polymerization) The polymerization reaction of 3-methyl-1-butene may be terminated by removing the monomer by distillation or filtration, or may be terminated by adding any polymerization terminator as necessary. As the polymerization terminator, a compound that reacts with a catalyst containing a compound having a transition metal atom of Group 4 of the periodic table is preferable. Examples of the polymerization terminator include compounds having active protons such as water, alcohol, primary amine, secondary amine, thiol, and Brestedt acid, as well as ethers, phosphines, tertiary amines, thioethers, carbon dioxide, and oxygen molecules. The polymerization terminator may be used alone or in combination of two or more kinds.

[0043] [Additives] If necessary, additives may be added to the polymerization reaction system. Examples of the additives include hydrogen, silane compounds such as methyl(cyclohexyl)dimethoxysilane, ester compounds such as ethyl benzoate, ether compounds such as 2,2-alkyl-substituted-1,3-dimethoxypropane, and amine compounds such as 2,2,6,6-tetramethylpiperidine. The additives may be used alone or in combination of two or more kinds.

[0044] (hydrogen) Hydrogen may be added to the polymerization reaction system. The addition method may be lump-sum addition, sequential addition, or continuous addition, but continuous addition is preferred from the viewpoint of obtaining polymer particles with a more uniform molecular weight. By adding hydrogen, the catalyst activity value (Y) is improved, and physical properties such as the melt viscosity of the polymer particles can also be adjusted. As the catalyst activity value (Y) is improved, the particle size of the polymer particles increases, so it is also possible to adjust the particle size of the polymer particles by adding hydrogen. From the viewpoint of obtaining 3-methyl-1-butene polymer particles having a predetermined particle size, the amount of hydrogen added is preferably 2.4 NL or less, more preferably 2.0 NL or less, and even more preferably 1.8 NL or less, in total, relative to 1 kg of monomer introduced into the polymerization reaction system.

[0045] [Removal of solid catalyst components] In the method for producing 3-methyl-1-butene polymer particles of the present embodiment, it is preferable to carry out a step of removing solid catalyst components contained in the polymer after the above-mentioned polymerization reaction. The method for removing the solid catalyst components is not particularly limited and can be a known method. For example, a method of adding an alcohol such as isobutanol or 2-propanol to the crude 3-methyl-1-butene polymer particles obtained by the above-mentioned polymerization reaction, stirring at a temperature of about 10 to 100 ° C., and then separating the polymer, and a method of adding an alcohol such as isobutanol or 2-propanol and a mineral acid such as hydrochloric acid or nitric acid to the crude 3-methyl-1-butene polymer particles obtained by the above-mentioned polymerization reaction, treating at a temperature of about 10 to 100 ° C., and then separating the polymer particles, etc. can be mentioned. The operation of removing the solid catalyst component may be carried out on the polymer slurry immediately after the polymerization reaction, or may be carried out after removing unreacted monomers and the reaction solvent from the polymer slurry by distillation or filtration, or may be carried out after carrying out the operation of removing the soluble polymer component described below.

[0046] [Removal of soluble components] The crude 3-methyl-1-butene polymer particles after the above-mentioned polymerization reaction may contain a polymerization component (hereinafter referred to as "soluble component") that is soluble in a heated hydrocarbon solvent (a hydrocarbon compound having 4 to 20 carbon atoms that may have a branched or cyclic structure). Although the details of the soluble component are not clear, the soluble component may be an oligomer component of the 3-methyl-1-butene polymer particles, a polymer component with low stereoregularity, a polymer component with a low content of structural units derived from 3-methyl-1-butene, or the like. Therefore, when the soluble component is contained in the crude 3-methyl-1-butene polymer particles, the method for producing the 3-methyl-1-butene polymer particles of this embodiment may include a step of removing the soluble component, or may be used for various applications without removing the soluble component. The method for removing the soluble components is not particularly limited and may be a known method. For example, the soluble components may be removed by adding a hydrocarbon solvent such as heptane to the obtained crude 3-methyl-1-butene polymer particles, stirring at a temperature of about 50 to 100°C, and then filtering the solution. In addition, since the soluble components dissolve in the unreacted monomers in the same manner as in the hydrocarbon solvent, they can also be removed by stirring the polymer slurry obtained by the above-mentioned polymerization reaction at a temperature of about 50 to 100°C and then filtering the solution. These removal operations may be repeated. The soluble components may be removed from the polymer slurry immediately after the polymerization reaction, or may be removed from the polymer slurry by distillation or filtration to remove unreacted monomers and reaction solvent.

[0047] [Drying of 3-methyl-1-butene polymer particles] In the method for producing 3-methyl-1-butene polymer particles of the present embodiment, after the above-mentioned coordination polymerization step and various steps which are performed as necessary, a step of drying the obtained 3-methyl-1-butene polymer particles may be performed. The drying is not particularly limited and may be a known method. For example, the drying may be performed by removing volatiles under conditions of normal pressure to 1 mmHg and 20 to 200° C. During drying, the 3-methyl-1-butene polymer particles may be left stationary, or may be fluidized by blowing air or an inert gas, or may be fluidized by a mechanical method such as an agitating rotary blade type dryer, a rotary type dryer, a continuous tray type dryer, or a fluidized type dryer.

[0048] <Applications of 3-methyl-1-butene polymer particles> The 3-methyl-1-butene polymer particles produced by the above-mentioned method can be applied to various fields by taking advantage of their excellent electrical properties, thermal properties, chemical resistance, etc. For example, the powder may be added to other resins as it is and used as a modifier for the resin, or may be used as a raw material for powder coating or a laser sinterable powder. Alternatively, like general thermoplastic resins, the polymer may be used as a raw material to which a molding is imparted by a known molding method, such as injection molding, extrusion molding, or compression molding.

[0049] <Fluid Dip Coating Method> As a method of powder coating using 3-methyl-1-butene polymer particles, there is a fluidized bed dip coating method, which is a method in which a preheated object to be coated is immersed in at least a part of a powder coating containing 3-methyl-1-butene polymer particles (hereinafter also referred to as powder coating) in a fluidized bed containing air from the bottom, and after removing the powder coating, the film of the powder coating attached to the object to be coated is heated.

[0050] From the standpoint of achieving continuous thin-film coating, the fluidized bed dip coating method is preferably a method in which air is introduced from the bottom of a fluidized bed containing powder paint at an average air permeability rate of 5 mm / min to 20 mm / min per unit area of ​​the bottom, and the surface-floating rate of the powder paint is set to 5% to 20%, and an object to be coated that has been preheated to a temperature in the range of melting point + 10°C to melting point + 30°C is immersed at least partially into the powder paint, and after removing it from the powder paint, the film of powder paint adhering to the object to be coated is heated.

[0051] In the fluidized bed dip coating method, the method of immersing the object to be coated in the powder paint and removing it from the powder paint can be any of the well-known methods, such as a method in which, while holding the object to be coated, the object is immersed in the powder paint from above the powder paint contained in a fluidized bed and then pulled up, or a method in which the object to be coated is dropped into the powder paint contained in a fluidized bed and then removed by vibration transport. The powder coating may be subjected to vibration before or during immersion of the article to be coated in the powder coating. While the object to be coated is immersed in the powder coating, the object to be coated may be stationary, or may be moved in a straight line or in an arc at, for example, 10 to 20 mm / sec. The workpiece may be partially or completely immersed in the powder paint, the method being selected depending on the area on which the coating film is to be formed.

[0052] From the viewpoint of realizing continuous thin-film coating, the average ventilation speed of the air introduced from the bottom of the fluidized bed is preferably 5 mm / min to 20 mm / min, more preferably 5 mm / min to 10 mm / min. When the average air permeability is 5 mm / min or more, the fluidity of the powder coating can be ensured, and the powder coating can be prevented from adhering discontinuously to the object to be coated, making it easier to obtain a continuous coating film. On the other hand, when the average air permeability is 20 mm / min or less, the necessary bulk density (approximately 80% or more) can be ensured, the density of the softened adhesive film becomes good, the occurrence of unevenness and defects can be prevented, and the quality of the coating film after melting becomes good. In this specification, the average aeration rate is the volume of air introduced from the bottom of the fluidization tank per unit time (minute) divided by the area of ​​the bottom of the fluidization tank (the air introduction surface).

[0053] From the viewpoint of realizing continuous thin film coating, the floating rate of the powder coating material is preferably 5% or more and 20% or less, and more preferably 10% or more and 15% or less. If the floating rate is 5% or more, the fluidity of the powder coating can be ensured, and the powder coating can be prevented from adhering discontinuously to the object to be coated, making it easier to obtain a continuous coating film. On the other hand, if the floating rate is 20% or less, the necessary bulk density (approximately 80% or more) can be ensured, the density of the softened adhesive film becomes good, the occurrence of unevenness and defects can be prevented, and the quality of the coating film after melting becomes good. In this specification, the floating rate is a value calculated by the following formula H. Formula H: Levitation rate (%) = (H2-H1) / H1×100 In the formula H, H1 represents the surface height of the powder paint contained in the fluidized bed when no air is introduced (i.e., the height from the bottom of the fluidized bed to the surface of the powder paint). H2 indicates the height of the surface of the powder paint contained in the fluidized bed when air is introduced (i.e., the height from the bottom of the fluidized bed to the surface of the powder paint).

[0054] The temperature of the object to be coated is preferably a temperature between the melting point of the powder coating material and the melting point + 20° C., from the viewpoint of realizing continuous thin film coating. By keeping the temperature of the workpiece within the above range, the necessary softening and adhesion of the powder coating occurs, making it easier to achieve continuous thin film coating. The temperature of the object to be coated is the surface temperature of the object to be coated when it is immersed in the powder paint.

[0055] The preheating temperature of the object to be coated is preferably the melting point + 10°C to the melting point + 30°C in order to achieve continuous thin film coating. If the preheating temperature is 10°C above the melting point, the temperature of the workpiece will not drop too much before the necessary softening and adhesion time of the powder paint has elapsed, and insufficient coating will be prevented.Similarly, if the preheating temperature is 30°C below the melting point, the generation of molten droplets on the workpiece surface at the start of immersion will be prevented, making it easier to obtain a continuous coating film.

[0056] The immersion time of the object to be coated is preferably from 5 to 20 seconds, more preferably from 5 to 10 seconds, from the viewpoint of productivity and realizing continuous thin film coating.

[0057] The temperature to which the powder coating film adhered to the object to be coated is preferably above the melting point and below the melting point + 20° C. The heating time for baking (baking time) is adjusted according to the heating temperature (baking temperature).

[0058] <Selective Sintering Additive Manufacturing Method> As a method for producing a three-dimensional object (molded body) using 3-methyl-1-butene-based polymer particles, a selective sintering additive manufacturing method can be mentioned. Specifically, the selective sintering additive manufacturing method can include (1) a thin layer forming step of forming a thin layer made of the above-mentioned polymer particles, (2) a preheating step of preheating the polymer particles, and (3) a laser light irradiation step of selectively irradiating the preheated thin layer made of the polymer particles with a laser light to form a modeled layer in which the resin particles contained in the polymer particles are melt-bonded to each other. Then, steps (1) to (3) are repeated multiple times to stack the modeled layers, thereby manufacturing a three-dimensional model. Note that either step (1) or step (2) may be performed first.

[0059] [Thin layer formation process (process (1))] In this step, a thin layer of the polymer particle material is formed. For example, the polymer particle material supplied from a polymer particle supply unit is spread evenly on the modeling stage by a recoater. The thin layer may be formed directly on the modeling stage, or may be formed on top of the polymer particle material that has already been spread or on top of a layer of a model that has already been formed.

[0060] The thickness of the thin layer is the same as the thickness of the desired modeled object layer. The thickness of the thin layer can be set arbitrarily depending on the accuracy of the three-dimensional object to be manufactured, but is usually 0.01 mm or more and 0.30 mm or less. By setting the thickness of the thin layer to 0.01 mm or more, it is possible to prevent the polymer particles of the lower layer from being melted and bonded by the laser light irradiation for forming the next modeled object layer. It is possible to spread the polymer particles uniformly. In addition, by setting the thickness of the thin layer to 0.30 mm or less, the energy of the laser light can be conducted to the lower part of the thin layer, and the polymer particles contained in the polymer particle material constituting the thin layer can be sufficiently melted and bonded throughout the entire thickness direction. From the above viewpoint, it is more preferable that the thickness of the thin layer is 0.01 mm or more and 0.10 mm or less. In addition, from the viewpoint of melting and bonding the polymer particles more sufficiently throughout the entire thickness direction of the thin layer and making it less likely that cracks will occur in the modeled object layer, it is preferable that the thickness of the thin layer is set so that the difference from the beam spot diameter of the laser light described later is within 0.10 mm.

[0061] [Preheating process (process (2))] In this step, the polymer particle material is preheated. As described above, either step (1) or step (2) may be performed first. For example, the polymer particle material may be preheated before the thin layer is formed, or the thin layer may be formed before the polymer particle material is preheated.

[0062] The preheating temperature for 3-methyl-1-butene polymer particles is preferably 250° C. or less, and more preferably 200° C. or more and 250° C. or less. By setting the preheating temperature to 250° C. or less, it is possible to suppress fusion between polymer particles during preheating.

[0063] In this case, the heating time is preferably 1 to 60 seconds, and more preferably 5 to 30 seconds. By setting the heating temperature and heating time within the above ranges, the cores in the polymer particles can be sufficiently softened or dissolved, and a three-dimensional object can be produced with a low laser irradiation dose.

[0064] [Laser light irradiation step (step (3))] In this process, a laser beam is selectively applied to the positions of the thin layer of preheated powder material where the model layer is to be formed, melting and bonding the polymer particles at the desired positions. The melted polymer particles (particularly the cores) melt with adjacent polymer particles to form the model layer. At this time, the polymer particles that receive the energy of the laser beam also melt and bond with the already formed model layer, resulting in adhesion between adjacent layers.

[0065] The wavelength of the laser light may be set within the range of wavelengths absorbed by the polymer particles. In this case, it is preferable to make the difference between the wavelength of the laser light and the wavelength at which the absorption rate of the polymer particles (particularly the shell material) is highest small. For example, 2 A laser beam having a wide wavelength band can be used, such as a laser, etc. The wavelength of the laser beam can be, for example, 0.8 μm or more and 12 μm or less.

[0066] The output power of the laser light may be set within a range that allows the temperature of the polymer particles to be increased at the scanning speed of the laser light described below. Specifically, it may be set to 5.0 W or more and 60 W or less. From the viewpoint of reducing the energy of the laser light, reducing the production cost, and simplifying the configuration of the production device, the output power of the laser light is preferably 30 W or less, and more preferably 20 W or less.

[0067] The scanning speed of the laser light may be set within a range that does not increase the manufacturing cost and does not excessively complicate the device configuration. Specifically, it is preferably set to 1 m / sec or more and 10 m / sec or less, more preferably 2 m / sec or more and 8 m / sec or less, and even more preferably 3 m / sec or more and 7 m / sec or less. The beam diameter of the laser light may be appropriately set depending on the precision of the three-dimensional object to be manufactured.

[0068] When manufacturing a three-dimensional object, the above-mentioned steps (1) to (3) are repeated any number of times, whereby object layers are stacked to obtain a desired three-dimensional object.

[0069] In order to prevent the strength of the three-dimensional object from decreasing due to oxidation of the polymer particles during melt bonding, it is preferable to carry out at least the step (3) under reduced pressure or in an inert gas atmosphere. -2 Pa or less, and -3 Pa or less. Examples of inert gases that can be used in the present embodiment include nitrogen gas and rare gases. Among these inert gases, nitrogen (N 2 ) gas, helium (He) gas, or argon (Ar) gas is preferred. From the viewpoint of simplifying the production process, it is preferred to carry out all of steps (1) to (3) under reduced pressure or in an inert gas atmosphere.

[0070] <Optional ingredients> When the 3-methyl-1-butene copolymer particles of this embodiment are used as a powder coating material or a material in the field of shaping by sintering a powder of the 3-methyl-1-butene copolymer particles, for example, a material for forming a molded body produced by the SLS method of a 3D printer, additives such as antioxidants, alkyl radical scavengers, antacids, fillers, light stabilizers, antistatic agents, flame retardants, pigments, polymerization inhibitors, heavy metal deactivators, ultraviolet absorbers, nucleating agents, clarifying agents, lubricants, fluorescent brighteners, and rust inhibitors may be contained as optional components. The optional components may be used alone or in combination of two or more. EXAMPLES

[0071] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.

[0072] <Measurement> Various physical properties were measured or evaluated by the following methods. [Content of structural units derived from comonomers] The content ratio of structural units derived from α-olefins (comonomers) other than 3-methyl-1-butene in the 3-methyl-1-butene polymer particles obtained in Examples 1 to 4 and Comparative Examples 1 to 3 was determined by IR measurement using an FT-IR (manufactured by Ailent Technologies, device name "cary 600 series FTIR spectrometer") as an analytical device by the ATR method, as follows. Bending vibration originating from the main chain methylene group of 3-methyl-1-butene homopolymer: 1,461 cm -1 and the bending vibration of 727 cm originating from the side chain methylene group of the homopolymer of α-olefin. -1 A calibration curve was created from the ratio of the peak area of ​​each resin to the peak area of ​​the other resins, and the ratio of each resin added. The IR measurement was performed on the 3-methyl-1-butene copolymer particles obtained in Examples 1 to 4, and the measured values ​​were inserted into the calibration curve to determine the content of structural units derived from α-olefins other than 3-methyl-1-butene.

[0073] [Melting point] The 3-methyl-1-butene polymer particles obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were heated from 30° C. to 320° C. at 10° C. / min under a nitrogen flow rate (100 mL / min) using a differential scanning calorimeter (TA Instruments, “DSC25”), held at 320° C. for 5 minutes, and then cooled to −70° C. at 10° C. / min. The peak temperature was measured when the temperature was raised to 320° C. at 10° C. / min after holding at −70° C. for 5 minutes, and the temperature was taken as the melting point.

[0074] [Dv50, Dv50 / Dn50, Dv'50, and Dv'50 / Dn'50] The Dv50, Dn50, Dv'50, and Dn'50 of the titanium solid catalysts obtained in Production Examples 1 to 5, and the 3-methyl-1-butene polymer particles obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were measured in accordance with JIS Z 8827-1:2008. A scanning electron microscope (Keyence Corporation's "3D Real Surface View Microscope VE-9800") was used as the measuring device, and the obtained images were analyzed using image analysis software "imageJ" (manufactured by the National Institutes of Health, USA). Dv50 / Dn50 and Dv'50 / Dn'50 were calculated from the obtained Dv50, Dn50, Dv'50, and Dn'50.

[0075] [Catalyst activity value (Y)] The amount (g) of the 3-methyl-1-butene polymer particles obtained in Examples 1 to 4 and Comparative Examples 1 to 3 divided by the amount (g) of the titanium solid catalyst component used in the production was defined as the catalytic activity value (Y).

[0076] Preparation of Titanium Solid Catalyst Component [Production Example 1] 47.6g (500mmol) of anhydrous magnesium chloride, 250ml of decane and 234ml (1.5mol) of 2-ethylhexyl alcohol were heated at 130℃ for 2 hours to obtain a homogeneous solution. The homogeneous solution obtained was cooled to room temperature (23℃) and then dropped into 2L (18mol) of titanium tetrachloride kept at -20℃ over 1 hour. After the dropwise addition, the temperature of the mixture was raised to 90℃ over 2 hours, and when it reached 90℃, 11.4mL (80mmol) of ethyl benzoate was added and kept at the same temperature for 2 hours while stirring. After the reaction for 2 hours was completed, the mixture was left to stand and the supernatant was removed. Decane and hexane were added to this, and the solid components were washed three times, then resuspended in 2L of titanium tetrachloride and heated again at 90℃ for 2 hours. After the reaction was completed, the mixture was left to stand again using decane and hexane, the supernatant was repeatedly removed, and the mixture was thoroughly washed until no free titanium compounds were detected in the washings. The resulting suspension was dried under reduced pressure at room temperature for 6 hours to obtain a titanium solid catalyst component (1). The composition of the obtained titanium solid catalyst component (1) was 5.4 mass % titanium, 58.6 mass % chlorine, 15.3 mass % magnesium, 9.7 mass % ethyl benzoate, and 11.0 mass % of the hydrocarbon solvent consisting of decane and hexane. Table 1 shows the Dv'50 and Dv'50 / Dn'50 of the titanium solid catalyst component (1).

[0077] [Production Example 2] A titanium solid catalyst component (2) was obtained in the same manner as in Production Example 1, except that the amount of ethyl benzoate was changed to 22.8 mL (160 mmol). The composition of the obtained titanium solid catalyst component (2) was 3.9 mass % of titanium, 57.0 mass % of chlorine, 16.4 mass % of magnesium, 15.2 mass % of ethyl benzoate, and 7.5 mass % of the hydrocarbon solvent consisting of decane and hexane. The Dv'50 and Dv'50 / Dn'50 of the titanium solid catalyst component (2) are shown in Table 1.

[0078] [Production Example 3] A titanium solid catalyst component (3) was produced in the same manner as in Production Example 1, except that the amount of ethyl benzoate was changed to 8.2 mL (57 mmol). The composition of the obtained titanium solid catalyst component (3) was 4.7 mass % titanium, 63.0 mass % chlorine, 17.4 mass % magnesium, 8.2 mass % ethyl benzoate, and 6.7 mass % of the hydrocarbon solvent consisting of decane and hexane. The Dv'50 and Dv'50 / Dn'50 of the titanium solid catalyst component (3) are shown in Table 1.

[0079] [Production Example 4] A titanium solid catalyst component (4) was produced in the same manner as in Production Example 1, except that the amount of ethyl benzoate was changed to 3.2 mL (22 mmol). The composition of the obtained titanium solid catalyst component was 5.0% by weight of titanium, 62.8% by weight of chlorine, 19.2% by weight of magnesium, 5.7% by weight of ethyl benzoate, and 7.3% by weight of a hydrocarbon solvent consisting of decane and hexane. The Dv'50 and Dv'50 / Dn'50 of the titanium solid catalyst component (4) are shown in Table 1.

[0080] [Production Example 5] A titanium solid catalyst component (5) was produced in the same manner as in Production Example 1, except that the amount of ethyl benzoate was changed to 30.5 mL (212 mmol). The composition of the obtained titanium solid catalyst component was 4.0% by weight of titanium, 55.5% by weight of chlorine, 17.2% by weight of magnesium, 18.9% by weight of ethyl benzoate, and 4.4% by weight of a hydrocarbon solvent consisting of decane and hexane. The Dv'50 and Dv'50 / Dn'50 of the titanium solid catalyst component (5) are shown in Table 1.

[0081] <Production of 3-methyl-1-butene polymer particles> [Example 1] In a 20L stainless steel autoclave, 8.0 kg of 3-methyl-1-butene, 0.6 kg of 1-decene, 50 g of triethylaluminum diluted with hexane to a concentration of 1 mol / L, and 11 g of titanium solid catalyst component (1) produced in Production Example 1 were added, and a coordination polymerization reaction was carried out at 70°C for 4 hours. After 4 hours, 200 g of isoamyl alcohol was injected to stop the reaction and drive out the excess unreacted monomer. Then, 2 kg of normal heptane was introduced, and the mixture was stirred at 60°C for 30 minutes, after which the solid matter was filtered off with a pressure filter. This operation was repeated twice, and then the solvent was changed from 2 kg of normal heptane to 3 kg of 2-propanol, and the same operation was repeated twice. 7.2 kg of the obtained crude polymer was placed in a 50 L container equipped with a stirrer, and then 8 kg of 1 mol / L hydrochloric acid and 16 kg of 2-propanol were added and stirred for 1 hour. This suspension was filtered by vacuum filtration and washed with 10 kg of 2-propanol. This crude polymer was placed in a 50 L container equipped with a stirrer, and then 20 kg of 2-propanol was added and stirred for 1 hour. This suspension was filtered by vacuum filtration and washed with 10 kg of 2-propanol. The washed polymer obtained was dried under reduced pressure at 80° C. for 2 days to obtain 3.0 kg of 3-methyl-1-butene polymer particles (X1). The measurement results of the obtained 3-methyl-1-butene polymer particles (X1) are shown in Table 1.

[0082] [Example 2] In the same manner as in Example 1, except that the titanium solid catalyst component (2) produced in Production Example 2 was used instead of the titanium solid catalyst component (1), 2.5 kg of 3-methyl-1-butene polymer particles (X2) were obtained. The measurement results of the obtained 3-methyl-1-butene polymer particles (X2) are shown in Table 1.

[0083] [Example 3] In the same manner as in Example 1, except that the titanium solid catalyst component (3) produced in Production Example 3 was used instead of the titanium solid catalyst component (1), 3.2 kg of 3-methyl-1-butene polymer particles (X3) were obtained. The measurement results of the obtained 3-methyl-1-butene polymer particles (X3) are shown in Table 1.

[0084] [Example 4] In the same manner as in Example 1, except that 4 g of the titanium solid catalyst component (3) produced in Production Example 3 was used instead of the titanium solid catalyst component (1), and hydrogen was continuously supplied at a rate of 40 mL / min during the polymerization reaction, 3.6 kg of 3-methyl-1-butene polymer particles were obtained. The measurement results of the obtained 3-methyl-1-butene polymer particles (X4) are shown in Table 1.

[0085] [Comparative Example 1] In the same manner as in Example 2, except that 4 g of the titanium solid catalyst component (2) was used and hydrogen was continuously supplied at a rate of 40 mL / min during the polymerization reaction, 2.6 kg of 3-methyl-1-butene polymer particles (Y1) was obtained. The measurement results of the obtained 3-methyl-1-butene polymer particles (Y1) are shown in Table 1.

[0086] [Comparative Example 2] In the same manner as in Example 1, except that 4 g of the titanium solid catalyst component (4) produced in Production Example 4 was used instead of the titanium solid catalyst component (1), and hydrogen was continuously supplied at a rate of 40 mL / min during the polymerization reaction, 3.3 kg of 3-methyl-1-butene polymer particles were obtained. The measurement results of the obtained 3-methyl-1-butene polymer particles (Y2) are shown in Table 1.

[0087] [Comparative Example 3] In the same manner as in Example 1, except that 11 g of the titanium solid catalyst component (5) produced in Production Example 5 was used instead of the titanium solid catalyst component (1), 3.0 kg of 3-methyl-1-butene polymer particles were obtained. The measurement results of the obtained 3-methyl-1-butene polymer particles (Y3) are shown in Table 1.

[0088] [Table 1]

[0089] It can be seen from Table 1 that the 3-methyl-1-butene polymer particles obtained in the examples have a predetermined particle size and a narrow particle size distribution. The 3-methyl-1-butene polymer particles in this embodiment are suitable as a powder coating material or a material for forming a molded body produced by the SLS method of a 3D printer.

Claims

1. 3-methyl-1-butene polymer particles having a particle diameter at 50% cumulative volume (Dv50) of 30 to 200 μm, and a ratio (Dv50 / Dn50) of the particle diameter at 50% cumulative volume (Dv50) to the particle diameter at 50% cumulative number (Dn50) of 2.00 or less.

2. 2. The 3-methyl-1-butene polymer particles according to claim 1, which have a melting point Tm of 265.0 to 290.0° C. as measured at a heating rate of 10° C. / min in differential scanning calorimetry.

3. 3. The 3-methyl-1-butene polymer particles according to claim 1, which are produced by a production method including a step of carrying out coordination polymerization.

4. 4. The 3-methyl-1-butene polymer particles according to claim 3, wherein the coordination polymerization is carried out using a solid catalyst supporting a compound having a transition metal atom of Group 4 of the periodic table.

5. 5. The 3-methyl-1-butene polymer particles according to claim 4, wherein a particle size (Dv'50 [μm]) at 50% cumulative volume of the solid catalyst and a catalytic activity value (Y) obtained by dividing the amount (g) of the 3-methyl-1-butene polymer particles produced by the production method by the amount (g) of the solid catalyst used in the production satisfy the following formula (1): 20≦Dv'50×Y^(1 / 3)≦150 (1)

6. 5. The 3-methyl-1-butene polymer particles according to claim 4, wherein the particle diameter at 50% of the cumulative volume of the solid catalyst (Dv'50) is 2.5 to 30 μm.

7. 6. The 3-methyl-1-butene polymer particles according to claim 5, wherein the catalytic activity value (Y) is 100 or more.

8. 5. The 3-methyl-1-butene polymer particles according to claim 4, wherein the coordination polymerization is carried out by adding the solid catalyst so that the amount of the metal atom is 0.00150 to 0.01000 parts by mass relative to 100 parts by mass of the 3-methyl-1-butene.

9. A method for producing 3-methyl-1-butene polymer particles, comprising the steps of supporting a compound having a transition metal atom of Group 4 of the periodic table and carrying out coordination polymerization using a solid catalyst that satisfies the following formula (1): 20≦Dv'50×Y^(1 / 3)≦150 (1) (In formula (1), Dv'50 is the particle size (μm) of the solid catalyst at 50% cumulative volume, and Y is the catalyst activity value (Y) obtained by dividing the amount (g) of the produced 3-methyl-1-butene polymer particles by the amount (g) of the solid catalyst used in the production.)

10. 10. The method for producing 3-methyl-1-butene polymer particles according to claim 9, wherein the particle diameter at 50% cumulative volume of the solid catalyst (Dv'50) is 2.5 to 30 μm.