Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
  • C08F4/652—Pretreating with metals or metal-containing compounds
  • C08F4/655—Pretreating with metals or metal-containing compounds with aluminium or compounds thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
  • H01M4/0433—Molding
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/043—Processes of manufacture in general involving compressing or compaction
  • H01M4/0435—Rolling or calendering
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/139—Processes of manufacture
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/17—Viscosity
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/18—Bulk density
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/24—Polymer with special particle form or size
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to ethylene polymer particles, a method for producing ethylene polymer particles, a stretched molded product, a method for producing a stretched molded product, and uses thereof.
• ultra-high molecular weight ethylene polymers which have extremely high molecular weights, are superior to general-purpose ethylene polymers in terms of impact resistance, wear resistance, chemical resistance, strength, etc., and have excellent characteristics as engineering plastics. have.
• ultra-high molecular weight ethylene-based polymers have poor fluidity when melted, so it is said that it is difficult to perform melt molding, which is a general resin molding method.
• melt molding which is a general resin molding method.
• a solid-phase stretching molding method has been developed in which the material is stretched after it has been stretched.
• Patent Document 1 describes a method for producing ultra-high molecular weight ethylene-based polymer particles with excellent stretchability.
• Patent Literature 2 describes a polyethylene powder that can suppress powder falling off of a colorant and has excellent fluidity.
• the ethylene-based polymer particles contain coarse particles during molding by the solid-phase stretching molding method or the like, it causes problems such as stagnation of the ethylene-based polymer particles during powder transfer.
• coarse particles may be present, uneven supply or clogging may occur due to poor fluidity of the powder, which may result in defective molding or uneven molding.
• the molding method including the step of spreading the powder evenly, coarse particles may be caught and dragged to cause defects. These molding unevenness and defects cause defects such as deterioration of physical properties and poor appearance of the molded product.
• a step of removing them by sieving is added, which takes time and effort. process is required. Therefore, a large number of coarse particles leads to an increase in production cost.
• Patent Literature 1 describes a production method capable of obtaining ultra-high molecular weight ethylene-based polymer particles having excellent stretchability while suppressing fouling.
• Patent Document 3 describes a method for efficiently producing olefin polymer particles having a relatively low molecular weight, a high bulk density and excellent particle properties without concomitant fouling.
• a binder is sometimes used to bind the inorganic materials together.
• a method for forming a compact using a binder for example, an inorganic material, a binder, and a solvent are mixed to form a slurry, the slurry is coated, and then the solvent is removed by heating (wet method). widely used.
• an electrode mixture layer used for electrodes.
• electrode active material layer used for electrodes.
• it is usually formed by a wet method in which a slurry containing an active material (inorganic material), a binder and a solvent is applied onto a current collector and the solvent is removed by heating.
• a dry method the formation of the electrode mixture layer by a dry method has been investigated. The formation of the electrode mixture layer by such a dry method is disclosed in Patent Document 4, for example.
• Japanese Patent No. 5689473 JP 2019-038931 A Japanese Patent No. 5796797 Japanese Patent Publication No. 2022-527458
• Patent Document 1 With the production method described in Patent Document 1, it is not possible to obtain ethylene-based polymer particles with excellent fluidity. Even with the polyethylene powder described in Patent Document 2, sufficient fluidity was not obtained, and moldability was not good.
• a baffle plate is generally installed in the reaction vessel for the purpose of more effectively achieving homogenization of the composition and reaction progress rate in the reaction system, and suppression of retention of products at the bottom.
• fouling and coarse particles were generated when the baffle plate was installed in the reaction tank. As described above, fouling promotes the generation of coarse particles, so further improvement is desired from the viewpoint of suppressing the generation of coarse particles in view of stable industrial production.
• binders Conventional materials that can be used as binders, including the binder described in Patent Document 4 and the polyethylene powder described in Patent Document 2, do not have sufficient binding properties (binding properties) for target components to which the materials bind. In some cases, the fluidity was not sufficient, and the handleability was not good.
• the problem to be solved by the first aspect of the present invention is to provide ethylene-based polymer particles with excellent fluidity.
• the problem to be solved by the second aspect of the present invention is to provide ultra-high-molecular-weight ethylene-based polymer particles that are excellent in industrial handleability and can be obtained at low cost, and that have few coarse particles and are excellent in stretching moldability. to provide.
• the problem to be solved by the third aspect of the present invention is to provide a method for producing ultra-high molecular weight ethylene polymer particles that are excellent in fluidity and stretch moldability while suppressing concurrent occurrence of fouling. .
• a problem to be solved by the fourth aspect of the present invention is to provide a binder that is excellent in handleability and binding properties.
• Configuration examples of the first aspect of the present invention are as described in [1] to [5] below.
• [1] Ethylene-based polymer particles having a specific surface area of more than 2.00 m 2 /g and 30.0 m 2 /g or less as determined by the BET method from the adsorption-desorption isotherm measured by the nitrogen gas adsorption method.
• D50 median diameter
• the ethylene polymer particles according to [1] which have a limiting viscosity [ ⁇ ] of 5 to 50 dl/g measured at 135°C in decalin solvent.
• Ethylene-based polymer particles having a specific surface area of more than 2.00 m 2 /g and 30.0 m 2 /g or less as determined by the BET method from the adsorption-desorption isotherm measured by the nitrogen gas adsorption method.
• Ethylene-based polymer particles wherein the acetone extract of the ethylene-based polymer particles contains a compound (F) having a molecular skeleton represented by the following general formula (I).
• R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
• R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
• [7] The ethylene polymer particles according to [6], wherein the compound (F) has a weight average molecular weight (Mw) of 500 or more and 30,000 or less.
• Mw weight average molecular weight
• [8] The ethylene polymer particles according to [6] or [7], wherein the content of the compound (F) is 6 ppm or more and 1,000 ppm or less.
• the amount of polymer particles that do not pass through the sieve is 20 mass.
• the method for producing a stretched molded product according to [12] which is obtained by a solid-phase stretch molding method.
• Configuration examples of the third aspect of the present invention are as described in [14] to [17] below.
• [14] A method for producing ethylene polymer particles having an intrinsic viscosity [ ⁇ ] of 5 to 50 dl/g measured at 135°C in decalin solvent, At least a step (1) of contacting a metal halide and an alcohol in a hydrocarbon solvent, and a step of contacting the component obtained in step (1) with an organoaluminum compound and/or an organoaluminumoxy compound.
• M represents titanium, zirconium, or hafnium
• m represents an integer of 1 to 4
• R 1 to R 5 may be the same or different, and may be 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 a containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be linked together to form a ring;
• R 6 is a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting only of primary or secondary carbon atoms, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, monocyclic or bicyclic selected from alicyclic hydrocarbon groups, aromatic hydrocarbon groups and halogen atoms of n is
• R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
• R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
• [15] The method for producing ethylene polymer particles according to [14], wherein the compound (F) has a weight average molecular weight of 500 or more and 30,000 or less.
• [16] The ethylene polymer particles according to [14] or [15], wherein the content of the metal halide-derived metal in the polymerization catalyst-containing liquid is 0.10 to 5.0 mmol/L. manufacturing method.
• [17] The method for producing ethylene polymer particles according to any one of [14] to [16], wherein the compound (F) is added at a temperature of 0 to 80°C.
• Configuration examples of the fourth aspect of the present invention are as described in [18] to [27] below.
• [18] A binder comprising the ethylene polymer particles according to any one of [1] to [3] and [6] to [11].
• [20] A molded article containing the binder according to [18] or [19] and an inorganic material.
• the compact according to [21], wherein the inorganic particles have an average particle size of 1 to 500 ⁇ m.
• An electrode comprising the molded article according to any one of [20] to [23] and a current collector.
• the electrode according to [24] obtained by a dry method.
• a lithium ion secondary battery comprising the electrode of [24] or [25] and an electrolyte.
• the ethylene polymer particles according to the first aspect of the present invention have excellent fluidity.
• the fluidity of the ethylene polymer particles is good, it becomes possible to supply the ethylene polymer particles uniformly into the molding container, resulting in good moldability. For this reason, very high-strength fibers can be obtained from the ethylene-based polymer particles according to the first aspect of the present invention in solid-phase drawing molding.
• the ethylene polymer particles according to the second aspect of the present invention contain a compound having a specific structural unit and have a specific specific surface area. As a result, sufficient fluidity can be obtained during transportation after polymerization, and transportation can be stably performed. Furthermore, when the ethylene-based polymer particles are stretch-molded, a stretch-molded product having high strength can be obtained. Thus, in the second aspect of the present invention, the two effects of the industrial advantage in the production of the ethylene polymer particles and the superiority of the physical properties of the ethylene polymer particles are highly balanced. be.
• the ethylene-based polymer particles according to the second aspect of the present invention are made of so-called ultra-high molecular weight polyethylene, and usually have a limiting viscosity [ ⁇ ], which will be described later.
• the olefin polymerization catalyst-containing liquid obtained through a specific process contains a compound having a specific structure as an essential component.
• fouling of the ethylene-based polymer particles to the walls of the polymerization tank, stirring blades, etc. can be minimized, and sufficient fluidity can be obtained during polymerization.
• the ethylene-based polymer particles obtained by this method are stretch-molded, a stretch-molded product having high strength can be obtained.
• the manufacturing method according to the third aspect of the present invention is highly advantageous from an industrial point of view.
• the obtained ethylene-based polymer particles have a predetermined intrinsic viscosity and are composed of so-called ultra-high molecular weight polyethylene, and stretched molded articles using the ethylene-based polymer particles are excellent in physical properties such as strength.
• the fourth aspect of the present invention it is possible to provide a binder with excellent handleability and binding properties.
• a binder capable of producing a molded article having excellent binding properties even by a dry method For example, it is possible to provide an electrode binder capable of producing an electrode mixture layer by a dry method.
• a molded article having excellent shape retention (self-standing) and mechanical strength (eg, tensile strength at break) can be produced by a dry method.
• ⁇ indicating a numerical range means “M or more and N or less” unless otherwise specified, for example, in the case of "M to N".
• (co)polymer is used as a concept encompassing both homopolymers and copolymers.
• the expression "structural unit derived from M” may be used, which means “structural unit corresponding to M", That is, it refers to a structural unit having a pair of bonds formed by opening the ⁇ bond that constitutes the double bond of M.
• ethylene-based polymer particles [1] ethylene-based polymer particles according to the first aspect of the present invention
• stretched molded products produced from the ethylene-based polymer particles [1] are described below. A more detailed description will be given.
• the ethylene polymer particles [1] according to the first aspect of the present invention have a specific surface area greater than 2.00 m 2 /g, which is determined by the BET method from the adsorption-desorption isotherm measured by the nitrogen gas adsorption method. , 30.0 m 2 /g or less.
• the specific surface area is preferably 2.50-28.0 m 2 /g, more preferably 3.00-26.0 m 2 /g. When the specific surface area is within the above range, the stretch moldability, particularly the solid phase stretch moldability, is excellent.
• the ethylene-based polymer particles [1] have a median diameter (D50) of 20 to 700 ⁇ m as determined by a laser diffraction scattering method.
• the median diameter (D50) is preferably 30 to 680 ⁇ m, more preferably 40 to 660 ⁇ m, still more preferably 220 to 660 ⁇ m.
• the fluidity is excellent when the median diameter (D50) is within the above range.
• the ethylene polymer particles [1] are formed by aggregates of fine particles.
• the median diameter is the average diameter of the aggregates (particles).
• the average particle size of fine particles can be determined by observation with a scanning electron microscope (SEM), but the median size is different from the average particle size of these fine particles.
• Particles for which the median diameter (D50) cannot be obtained by the laser diffraction/scattering method because the particle size is not within the measurable range of the measuring device are ethylene polymer particles [1]. isn't it.
• ethylene polymer particles having a median diameter within the above range In order to obtain ethylene polymer particles having a median diameter within the above range, polymerization conditions are adjusted in the polymerization step so as to obtain a median diameter within the above range, and ethylene polymer particles having a median diameter within the above range are obtained. Coalesced particles can be obtained, or ethylene polymer particles having a median diameter within the above range may be obtained by pulverizing the ethylene polymer particles having a median diameter larger than the above range. Setting the median diameter within the above range may be performed in the polymerization step or in the post-treatment step.
• the ethylene polymer particles [1] preferably have a limiting viscosity [ ⁇ ] of 5 to 50 dl/g, more preferably 6 to 50 dl/g, measured at 135°C in decalin solvent, and more preferably 7 to 50 dl/g. More preferably 50 dl/g.
• a limiting viscosity [ ⁇ ] of 5 to 50 dl/g, more preferably 6 to 50 dl/g, measured at 135°C in decalin solvent, and more preferably 7 to 50 dl/g. More preferably 50 dl/g.
• the ethylene polymer particles [1] preferably have a bulk density of 0.01 to 0.20 g/mL, more preferably 0.02 to 0.20 g/mL, and more preferably 0.03 to 0.2 g/mL. More preferably 20 g/mL. When the bulk density is within the above range, fluidity is further improved.
• the ethylene-based polymer that constitutes the ethylene-based polymer particles [1] is an ethylene homopolymer or a copolymer of ethylene and other monomers.
• Examples of other monomers include linear or branched ⁇ -olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and polar monomers. , ⁇ , ⁇ -unsaturated carboxylic acid esters, unsaturated glycidyl esters, vinylcyclohexane, dienes, polyenes and aromatic vinyl compounds.
• Examples of the ⁇ -olefin include propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 3-methyl-1-pentene. , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like.
• cyclic olefins examples include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned.
• Examples of the polar monomer include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride, and the like.
• Examples include ⁇ , ⁇ -unsaturated carboxylic acids and ⁇ , ⁇ -unsaturated carboxylic acid metal salts such as sodium salts, potassium salts, lithium salts, zinc salts, magnesium salts and calcium salts thereof.
• Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and acrylic acid 2.
• -ethylhexyl methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and the like.
• unsaturated glycidyl ester examples include vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, itacon Unsaturated glycidyl esters such as acid monoglycidyl esters and the like can be mentioned.
• the dienes and polyenes include cyclic or chain compounds having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms and two or more double bonds.
• aromatic vinyl compound examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene.
• styrene mono- or polyalkylstyrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; Phenylpropylene, 4-phenylpropylene, ⁇ -methylstyrene can be mentioned.
• the repeating unit derived from ethylene is 99.5 mol% or more.
• the content of repeating units derived from other monomers can be measured by known measurement methods such as nuclear magnetic resonance (NMR) spectrometry and infrared absorption spectrometry.
• the ethylene-based polymer is preferably an ethylene homopolymer from the viewpoint of increasing the degree of crystallinity and from the viewpoint of stretchability in solid-phase stretching molding.
• a copolymer of ethylene and propylene or the like is preferable.
• the ethylene-based polymer, or the ethylene-based polymer constituting the ethylene-based polymer particles [2] or [3] described later, respectively, contains at least one or more biomass-derived monomers (ethylene, other monomer).
• the same kind of monomers constituting the polymer may be only biomass-derived monomers, may be only fossil fuel-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers.
• Biomass-derived monomers are monomers derived from any renewable natural raw material and its residues, such as plant- or animal-derived, including fungi, yeast, algae and bacteria, and containing 1 ⁇ C isotope as carbon.
• the biomass carbon concentration (unit: pMC) measured according to ASTM D6866 is about 100 pMC.
• Biomass-derived monomers (other monomers such as ethylene and ⁇ -olefins) can be obtained, for example, by conventionally known methods.
• these ethylene-based polymers it is preferable for these ethylene-based polymers to contain structural units derived from biomass-derived monomers, from the viewpoint of reducing environmental loads (mainly reducing greenhouse gases). If the polymer production conditions such as the polymerization catalyst, polymerization process, and polymerization temperature are the same, even if the raw material monomer is a (co)polymer containing a biomass-derived monomer, the 14 C isotope will be reduced to 1 ⁇ 10 ⁇ 12 .
• the molecular structure other than the ratio of about 10 -14 is equivalent to that of a (co)polymer composed of fossil fuel-derived monomers. Therefore, the performance is assumed to be unchanged.
• the production method of the ethylene polymer particles [1] is not particularly limited, but it can be produced based on the method described in Patent Document 1 mentioned above.
• a method of suppressing aggregation by increasing power and linear velocity during stirring in the polymerization step for example, (1) a method of suppressing aggregation by increasing power and linear velocity during stirring in the polymerization step, (2) polymerization A method of adding an antistatic agent or the like to the process to suppress aggregation, (3) a method of crushing in a post-treatment step after polymerization, and the like can be adopted.
• a stretched molded article can be obtained by stretching the ethylene-based polymer particles [1].
• the stretched molded article is obtained, for example, by molding the ethylene polymer particles [1] by a known stretch molding method for polyethylene.
• the ethylene-based polymer particles [1] have good fluidity and therefore good moldability. Also, if the fluidity is excellent, it is possible to obtain a fiber having a very high mechanical strength in, for example, solid-phase drawing molding.
• the above-mentioned stretched molded article tends to yield a high-strength molded article by using ethylene-based polymer particles with a high intrinsic viscosity [ ⁇ ].
• Solid-phase stretching molding is a molding method that does not use a solvent, so molding equipment is relatively simple, and it is a molding method that has little adverse effect on the environment. Therefore, it is considered that providing a stretched molded product by such a method will contribute more to society.
• the ethylene-based polymer particles [1] exhibit extremely high drawing performance when solid-phase drawing is performed, so it is possible to obtain fibers, films, sheets, and biomaterials such as bone substitute materials with high strength.
• the ethylene-based polymer particles [1] are press-bonded at a pressure of 1 MPa or more to form a sheet, which is stretched at a relatively high temperature or stretched while applying pressure using rolls or the like. method.
• the temperature at which the molding is carried out in the crimping step, the stretching step, etc. is preferably below the melting point of the ethylene polymer particles used, but may be above the melting point as long as melt flow does not substantially occur. .
• the temperature range is such that the upper limit is about 5°C higher than the melting point of the ethylene polymer particles used and the lower limit is about 30°C lower than the melting point.
• the draw ratio is more preferably 80 times or more, still more preferably 100 times or more, and particularly preferably 120 times or more.
• the stress during stretching is preferably 30 MPa or less, more preferably 25 MPa or less, even more preferably 23 MPa or less, even more preferably 20 MPa or less, and particularly preferably 16 MPa or less.
• the stretched molded article according to the first aspect of the present invention can be molded at a high draw ratio, so it is expected to have a high tensile modulus and tensile strength.
• the tensile elastic modulus of the obtained stretched molded product is preferably 80 GPa or more, more preferably 120 GPa or more, and particularly preferably 140 GPa or more.
• the strength of the obtained stretched molded product is preferably 1 GPa or more, more preferably 2 GPa or more, still more preferably 2.5 GPa or more, and particularly preferably 3 GPa or more.
• ethylene-based polymer particles [2] ethylene-based polymer particles according to the second aspect of the present invention
• stretched molded articles produced from the ethylene-based polymer particles [2] stretched molded articles produced from the ethylene-based polymer particles [2]
• the manufacturing method thereof will be described in further detail.
• the ethylene polymer particles [2] according to the second aspect of the present invention have a specific surface area of more than 2.00 m 2 /g and 30.0 m 2 /g or less, and the ethylene polymer particles [2] 2] is characterized in that the acetone extract contains a compound (F) having a molecular skeleton of general formula [I].
• the specific surface area means the total specific surface area obtained by summing all the specific surface areas obtained by the BET method from the adsorption/desorption isotherm measured by the nitrogen gas adsorption method, and is usually larger than 2.00 m 2 /g, 30.0 m 2 /g or less, preferably 2.50 to 28.0 m 2 /g, more preferably 3.00 to 26.0 m 2 /g, still more preferably 4.00 to 20.0 m 2 /g , and still more preferably 5.00 to 18.0 m 2 /g.
• the stretch moldability particularly the solid-phase stretch moldability, is excellent.
• the present inventors have found that the total specific surface area of the ethylene-based polymer particles is large and is within the above range, so that even when the molecular weight of the ethylene-based polymer is increased, the adhesion between the particles is good, and the It was found that a high-strength stretch-molded product can be obtained because solid-phase stretch molding at a draw ratio becomes possible.
• the acetone extract of the ethylene-based polymer particles is a component that is eluted into acetone after the ethylene-based polymer particles are brought into contact with acetone.
• the components that are eluted into acetone are the catalysts, additives, and the like used in the polymerization operation stage among the constituent components of the ethylene-based polymer particles.
• Components such as additives used after polymerization are also included in the acetone extract.
• the acetone extract contains a compound (F) having a molecular skeleton of general formula (I) below.
• the molecular skeleton represented by general formula (I) may be referred to as "oxyalkylene skeleton”.
• R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
• alkyl groups having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group and n- Linear or branched alkyl groups such as hexyl group, n-heptyl group, n-octyl group and n-nonyl group can be exemplified.
• R is a hydrogen atom or a methyl group, it is preferable because the polymerization activity and the effect of suppressing the generation of coarse particles are excellent, and it is more preferably a hydrogen atom.
• the compound (F) containing an oxyalkylene skeleton is a compound derived from an antistatic agent, which is one of the additives added at the stage of the polymerization operation. Further, it may be added after the polymerization. Therefore, the content of the compound (F) in the ethylene-based polymer particles can be adjusted by adjusting the concentration of the compound (F) during the polymerization operation, and can be adjusted by adding the compound (F) after the polymerization. may Since the presence of the compound (F) improves the fluidity of the powder, the powder can be shaped uniformly. Furthermore, by adding the compound (F) during polymerization rather than adding the compound (F) after polymerization, the compound (F) penetrates into the inside of the polymer particles, and a stretched molded product having excellent stretch moldability and strength is obtained. can get.
• the compound (F) preferably takes a form in which a hydrogen atom is bonded to the oxygen of the oxyalkylene skeleton represented by the general formula (I), and particularly preferably, the following general formulas [F1], [F2] or It is a compound having one or two or more skeletons represented by [F3] in the molecule, and these can be used without limitation.
• R has the same definition as R described in formula (I) above.
• R" represents the same atom or group as R, n and m are integers of 0 or 1, p is an integer of 1 or 2, and the sum of m and p is 2 It is preferable that m is 0 and p is 2 from the viewpoint of the polymerization activity and the effect of suppressing the generation of coarse particles.
• Examples of the compound containing the skeleton represented by the general formula [F1] include polyoxyalkylene compounds represented by the following general formulas [F1-1] and [F1-2].
• R b , R b′ and R b′′ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably a hydrogen atom or a methyl group, and a hydrogen atom. is more preferable.
• n, n', n'' are each independently an integer of 0 or 1
• k, k''' represent the average number of repeating units and range from 1 to 100
• k', k'' are the average It represents the number of repeating units and ranges from 0 to 100.
• R a is selected from a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms and an acyl group having 1 to 20 carbon atoms.
• alkyl group having 1 to 12 carbon atoms are the same as those exemplified in the description of the alkyl group having 1 to 12 carbon atoms.
• q is an integer of 1 to 4
• R c is selected from a hydrocarbon group having 1 to 12 carbon atoms, an oxygen-containing group, or a nitrogen-containing group.
• the hydrocarbon group having 1 to 12 carbon atoms is an aliphatic or aromatic hydrocarbon group to which q substituents described in [F1-2] are bonded. Examples of the hydrocarbon group having 1 to 12 carbon atoms include, when q is 1, the same hydrocarbon groups as exemplified for R a in the formula [F1-1].
• ethylene structure (--CH 2 CH 2 --), 1,2-propylene structure (--CH(CH 3 )CH 2 --), 1,3-propylene structure (--CH 2 CH 2 CH 2 -), 1,4-butylene structure (-CH 2 CH 2 CH 2 -), 1,2-benzenediyl structure, 1,3-benzenediyl structure, 1,4-benzenediyl structure and the like.
• examples include a 1,2,3-propanetriyl structure.
• examples include a 1,2,4,5-benzenetetrayl structure.
• Oxygen-containing groups include groups having 1 to 12 carbon atoms containing at least one selected from an ether bond and a carbonyl group.
• oxygen-containing groups include the structure derived from ethylene glycol (O--CH 2 CH 2 --O), the structure derived from propylene glycol (O--CH(CH 3 )CH 2 --O), the structure derived from 1,3-propanediol.
• R c is an oxygen-containing group
• at least one selected from an ether bond and a carbonyl group is preferably bonded to a structure having q repeating units, in which case q is an ether in the oxygen-containing group It is preferably an integer from 1 to 4 which is equal to or less than the sum of bonds and carbonyl groups.
• q is an integer smaller than the sum of ether bonds and carbonyl groups in the oxygen-containing group, and when the end of the oxygen-containing group is an ether bond and a carbonyl group, the repeating unit bonded to the oxygen atom is q Groups other than the structure of include a hydrogen atom.
• nitrogen-containing groups include the ethylenediamine structure (N-- CH.sub.2CH.sub.2 --N), the propylenediamine structure (N--CH( CH.sub.3 ) CH.sub.2 --N), the 1,3-propanediamine structure (N-- CH.sub.2 CH 2 CH 2 —N), 1,4-butanediamine structure (N—CH 2 CH 2 CH 2 CH 2 —N), o-phenylenediamine structure, m-phenylenediamine structure, and p-phenylenediamine structure
• groups containing at least one selected structure consisting of (only) one structure selected from).
• R c is a nitrogen-containing group
• the nitrogen atom in the nitrogen-containing group is bonded to a structure having q repeating units, and q is an integer of 1 to 3.
• a group other than the structure having q repeating units bonded to a nitrogen atom includes a hydrogen atom.
• q is preferably 4 from the viewpoint of the polymerization activity and the effect of suppressing the generation of coarse particles.
• R c is preferably a nitrogen-containing group from the viewpoint of polymerization activity and effect of suppressing the generation of coarse particles, and contains at least one structure selected from an ethylenediamine structure, a propylenediamine structure, and a 1,3-propanediamine structure (from A group consisting of (only) one selected structure is more preferred, a group containing an ethylenediamine structure (N—CH 2 CH 2 —N) is more preferred, and a group consisting of an ethylenediamine structure (only) is even more preferred.
• polyoxyalkylene compounds examples include polyethylene glycols such as triethylene glycol, tetraethylene glycol, hexaethylene glycol and heptaethylene glycol; triethylene glycol monoalkyl ethers, tetraethylene glycol monoalkyl ethers and hexaethylene glycol; Polyethylene glycol monoalkyl ethers such as monoalkyl ether and heptaethylene glycol monoalkyl ether; Polyethylene glycol monoalkyl ethers such as triethylene glycol monoalkyl ester, tetraethylene glycol monoalkyl ester, hexaethylene glycol monoalkyl ester and heptaethylene glycol monoalkyl ester; alkyl ester; polypropylene glycol monoalkyl ether such as tripropylene glycol dialkyl ether, tripropylene glycol monoalkyl ether, tetrapropylene glycol monoalkyl ether, hexapropylene glycol monoalkyl mono
• the aliphatic diethanolamide described in the aforementioned Patent Document 2 can be preferably exemplified.
• the tertiary amine compound described in Patent Document 2 can also be preferably exemplified.
• the weight average molecular weight (Mw) of the compound (F) measured by gel permeation chromatography (GPC) is preferably 500 or more and 30,000 or less, more preferably 1,000 or more and 25,500 or less, It is more preferably 1,500 or more and 20,000 or less, and particularly preferably 1,500 or more and 10,000 or less.
• Mw is within the above range, the ethylene polymer particles are excellent in stretch moldability and the amount of coarse particles generated can be reduced, so that the fluidity in the pipe during transfer is improved and uniform molding is achieved in stretch molding. you get a body On the other hand, if the Mw is small, there is a risk of bleeding out during molding, resulting in poor quality.
• the compound (F) include the “ADEKA Pluronic (registered trademark)” series manufactured by ADEKA Corporation.
• ADEKA Pluronic (registered trademark) L-71 (Mw: 3,760) “ADEKA Pluronic (registered trademark) L-72 (Mw: 4,700)”
• Adeka Pluronic (registered trademark) L-31 (Mw: 1,700) “Adeka Pluronic (registered trademark) P-85 (Mw: 7,430)”
• ADEKA Pluronic (registered trademark) F-88 (Mw: 19,300) "ADEKA Pluronic (registered trademark) 17-R2 (Mw: 3,310)”
• the oxyarene skeleton can be identified by a known analytical method such as nuclear magnetic resonance (NMR) spectrum.
• NMR nuclear magnetic resonance
• the content of the compound (F) eluted from the ethylene-based polymer particles [2], calculated from liquid chromatography-mass (LC-MS) analysis described later, is preferably 6 ppm or more relative to the ethylene-based polymer particles. 1,000 ppm or less.
• the content of the compound (F) is within the above range, the ethylene polymer particles can be stretch-molded at a high draw ratio, and the generation of coarse particles can be suppressed, so that the fluidity in the pipe during transportation is improved. improves.
• it is more preferably 8 ppm or more and 600 ppm or less, and still more preferably 10 ppm or more and 400 ppm or less.
• the coarse particles in the present invention mean particles of 1 mm or more, and when sieved with a mesh sieve of 1 mm ⁇ 1 mm at a shaking time of 10 minutes, an amplitude of 0.5 mm, and an interval of 15 seconds, they do not pass through the sieve. refers to particles. If the ethylene polymer particles contain many coarse particles of 1 mm or more, sufficient fluidity cannot be obtained during transfer after polymerization, and valves, pumps, strainers, etc. may be clogged. From the viewpoint of preventing the above problems, the content of coarse particles (coarse particle amount) in the ethylene polymer particles [2] is usually 20% by mass or less, preferably 15% by mass or less, and 10% by mass or less.
• 7% by mass or less is even more preferable, 3% by mass or less is particularly preferable, and 1.5% by mass or less is particularly preferable. If there are few coarse particles, the transportability of the powder in the processing process is good, so the powder can be shaped uniformly, and a stretched molded product excellent in stretchability and strength can be obtained.
• ethylene polymer particles having a very high specific surface area can be produced by using a magnesium halide (preferably MgCl 2 ) during production.
• a portion of the magnesium halide used during manufacture is usually included in the ethylene-based polymer particles, the magnesium content of which corresponds to the concentration of magnesium halide during manufacture.
• the content of magnesium in the ethylene polymer particles [2] is preferably 10 to 2,000 ppm, more preferably 20 to 1,500 ppm, even more preferably 30 to 1,000 ppm. Within the above range, the ethylene-based polymer particles [2] are excellent in powder fluidity and stretch moldability.
• the ethylene polymer particles [2] preferably have a limiting viscosity [ ⁇ ] of 5 to 50 dl/g, more preferably 7 to 50 dl/g, measured at 135°C in decalin solvent, and more preferably 10 to 50 dl/g. 45 dl/g is more preferred, 15 to 45 dl/g is particularly preferred, and 20 to 45 dl/g is particularly preferred.
• the intrinsic viscosity [ ⁇ ] is within the above range, the fluidity of the ethylene polymer particles is further improved. If the intrinsic viscosity [ ⁇ ] is lower than the above range, the strength of the resin will be low, and if the intrinsic viscosity [ ⁇ ] is higher than the above range, stretch molding may become difficult.
• ethylene-based polymers having an intrinsic viscosity [ ⁇ ] within the above range usually tend to have extremely high molecular weights. It can be said that it consists of
• the ethylene polymer particles [2] preferably have a bulk density (BD) of 0.01 to 0.20 g/mL, more preferably 0.02 to 0.18 g/mL. It is preferably 0.03 to 0.16 g/mL, and particularly preferably 0.04 to 0.15 g/mL.
• BD bulk density
• the specific surface area tends to be smaller than the above range, and when the bulk density is too low or too high compared to the above range, the fluidity of the ethylene polymer particles deteriorates. There is a tendency.
• the ethylene polymer constituting the ethylene polymer particles [2] is an ethylene homopolymer or a copolymer of ethylene and a linear or branched ⁇ -olefin having 3 to 20 carbon atoms. and preferably an ethylene homopolymer.
• the ⁇ -olefin having 3 to 20 carbon atoms to be copolymerized with ethylene is preferably an ⁇ -olefin having 3 to 10 carbon atoms, more preferably an ⁇ -olefin having 3 to 8 carbon atoms.
• linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene; 4-methyl-1-pentene, 3-methyl-1-pentene, 3 -methyl-1-butene, preferably propylene, 1-butene, 1-hexene, 4-methyl-1-pentene.
• the ⁇ -olefins may be used singly or in combination of two or more.
• the content of ⁇ -olefin that is, the molar ratio of repeating units derived from ⁇ -olefin copolymerized with ethylene to all repeating units is 5 mol% or less, preferably 2 mol% or less, more preferably 0.5 mol% or less. .
• the ethylene-based polymer constituting the ethylene-based polymer particles [2] is an ethylene homopolymer
• a copolymer of ethylene and an ⁇ -olefin if the content of the ⁇ -olefin is more than the above-mentioned range, branches derived from the ⁇ -olefin may become structural defects and sufficient strength may not be obtained.
• the ethylene content in the ethylene-based polymer can be measured by known measurement methods such as nuclear magnetic resonance (NMR) spectrum measurement and infrared absorption spectrum measurement.
• the ethylene-based polymer particles [2] are preferably produced by the method for producing ethylene-based polymer particles according to the third aspect of the present invention, which will be described later.
• the stretched molded product according to the second aspect of the present invention can be obtained by stretching the ethylene-based polymer particles [2].
• the stretch-molded article is obtained, for example, by molding the ethylene-based polymer particles [2] by a known stretch-molding method for polyethylene.
• the ethylene-based polymer particles [2] have good fluidity, so that they have good moldability. If the moldability is good, for example, it is possible to obtain a stretch-molded product with very high mechanical strength in solid-phase stretch molding.
• the ethylene-based polymer particles [2] can be dissolved or mixed in a suitable solvent or plasticizer to prepare a gel-like mixture, and a molded product having high strength can be obtained by using a known gel-spinning technique. .
• a stretched molded article made of ethylene polymer particles [2] tends to obtain a molded article with even higher strength by using so-called ultra-high molecular weight ethylene polymer particles with a high intrinsic viscosity [ ⁇ ].
• a solid phase stretched molded article molded by a solid phase stretched molding method is particularly preferable. Since the solid-phase stretch molding method is a method of molding without using a solvent, the molding equipment is relatively simple, and the molding method has little adverse effect on the environment. Therefore, it is considered that providing a stretched molded product by such a method will contribute more to society.
• the ethylene-based polymer particles [2] exhibit extremely high stretching performance when solid-phase stretching molding is performed, making it possible to obtain high-strength fibers, films, sheets, biomaterials such as bone substitute materials, and the like.
• the ethylene-based polymer particles [2] are also useful for producing microporous membranes.
• the thickness of the microporous membrane varies depending on the application, it is usually 0.1-1000 ⁇ m, preferably 1-500 ⁇ m.
• the thickness of the microporous membrane can be measured with a commercially available film thickness gauge.
• the microporous membrane preferably has pores.
• the porosity of the microporous membrane is preferably 30 to 95%, more preferably 40 to 90%, depending on the application. Such an aspect is preferable from the viewpoint of gas permeability and mechanical strength.
• known conditions can be used without limitation, except that the ethylene-based polymer particles [2] are used.
• it can be produced under the same conditions as those of the solid phase stretch molding method for the stretch molded product according to the first aspect of the present invention.
• the draw ratio is preferably 80 times or more, more preferably 100 times or more, and still more preferably 120 times or more. When the draw ratio is within the above range, it can be said that the draw ratio is sufficiently high.
• the stress during stretching is preferably 30 MPa or less, more preferably 25 MPa or less, even more preferably 23 MPa or less, even more preferably 20 MPa or less, and particularly preferably 16 MPa or less.
• the stretched molded article according to the second aspect of the present invention can be molded at a high draw ratio as described above, so it is expected to have a high tensile modulus and tensile strength.
• the tensile elastic modulus of the obtained stretched molded product is preferably 80 GPa or more, more preferably 120 GPa or more, and even more preferably 140 GPa or more.
• the strength of the obtained stretched molded product is preferably 1 GPa or more, more preferably 2 GPa or more, still more preferably 2.5 GPa or more, and particularly preferably 3 GPa or more.
• the method for producing a stretched molded product according to the second aspect of the present invention is a model model using a small amount of sample, such as rolling with a capillary rheometer described in Patent Document 1 and then stretching using a tensile tester.
• molding is performed by filling a long mold with ethylene-based polymer powder and compressing it, or by compressing the powder spread evenly with a doctor blade. For example, if coarse particles or agglomerated particles are present in the step of spreading the powder evenly, the coarse particles are caught and dragged during the scraping operation for making the ethylene polymer particles uniform in thickness. In some cases, the traces become defects, making it impossible to obtain a uniform molded product.
• the method for producing ethylene-based polymer particles according to the third aspect of the present invention (hereinafter also referred to as "this production method") will be described in more detail below.
• the ethylene-based polymer particles in the present production method mean polymer particles containing ethylene as a main component, and include ethylene homopolymer particles and copolymer particles of ethylene and other monomers.
• This production method is characterized by including the following steps [ ⁇ ] and [ ⁇ ].
• the ethylene-based polymer particles produced by this production method have a predetermined intrinsic viscosity [ ⁇ ].
• step (1) At least a step (1) of contacting a metal halide and an alcohol in a hydrocarbon solvent, and a step of contacting the component obtained in step (1) with an organoaluminum compound and/or an organoaluminumoxy compound.
• Step of Producing Particles First, the step [ ⁇ ] of producing the olefin polymerization catalyst-containing liquid used in the production method of the third aspect of the present invention will be described below.
• the step [ ⁇ ] is a step of producing an olefin polymerization catalyst-containing liquid.
• the steps include the following steps ⁇ i> to ⁇ iii>, and the step ⁇ iii> is performed at a predetermined timing.
• ⁇ i> At least a step (1) of contacting a metal halide and an alcohol in a hydrocarbon solvent, and contacting the component obtained in step (1) with an organoaluminum compound and/or an organoaluminumoxy compound.
• ⁇ ii> the suspension obtained in the step ⁇ i> and a transition metal compound (B) represented by the following general formula (I): Step of contact ⁇ iii> Step of adding compound (F) containing a molecular skeleton represented by the following general formula (II) Steps ⁇ i> to ⁇ iii> will be described in detail below.
• Step ⁇ i> is a step of obtaining a suspension via at least the following two steps.
• a step of contacting a metal halide with an alcohol in a hydrocarbon solvent (2) A step of contacting the component obtained in step (1) with an organoaluminum compound and/or an organoaluminumoxy compound below , the content of each step and the compounds used in each step.
• Step (1) is a step of contacting a metal halide and an alcohol in a hydrocarbon solvent.
• the order in which they are brought into contact is not particularly limited, and they may be brought into contact at once or sequentially.
• the step (1) is a step of contacting a metal halide and an alcohol in a hydrocarbon solvent to form an alcohol complex of the metal halide and forming a finely dispersed solution of the alcohol complex in the hydrocarbon solvent.
• Step (1) is usually performed under normal pressure heating or pressurized heating.
• the temperature up to the boiling point of the hydrocarbon solvent used can be arbitrarily selected, and when heating under pressure, up to the boiling point of the hydrocarbon solvent or alcohol used under pressure. can be arbitrarily selected.
• the method of contacting the metal halide and the alcohol in the hydrocarbon solvent in step (1) is not particularly limited, and includes, for example, ordinary stirring and mixing.
• stirring and mixing a generally used known stirrer or the like may be used.
• metal halide Preferred examples of the metal halides include ion-binding compounds having a CdCl 2 -type or CdI 2 -type layered crystal structure. Specific examples of compounds having a CdCl 2 -type crystal structure include CdCl 2 , MnCl 2 , FeCl 2 , CoCl 2 , NiI 2 , NiCl 2 , MgCl 2 , ZnBr 2 and CrCl 3 .
• compounds having a CdI2 type crystal structure include CdBr2 , FeBr2 , CoBr2, NiBr2 , CdI2 , MgI2 , CaI2 , ZnI2 , PbI2 , MnI2 , FeI2 , CoI2 , Mg(OH) 2 , Ca(OH) 2 , Cd(OH) 2 , Mn(OH) 2 , Fe(OH) 2 , Co(OH) 2 , Ni(OH) 2 , ZrS4 , SnS4 , TiS 4 , PtS 4 and the like.
• CdBr2 , FeBr2 , CoBr2, NiBr2 , CdI2 , MgI2 , CaI2, ZnI2 , PbI2 , MnI2 , FeI2 , CoI2 , CdCl2 , MnCl2 and FeCl2 are preferred.
• CoCl 2 , NiI 2 , NiCl 2 , MgCl 2 and ZnBr 2 more preferably MgI 2 and MgCl 2 which are magnesium halides, and particularly preferably MgCl 2 . 1 type may be used for a metal halide and 2 or more types may be used for it.
• the ion-binding compound as described above may be finally contained in the catalyst, and the ion-binding compound itself does not necessarily have to be used.
• compounds capable of forming an ion-binding compound may be used to form the ion-binding compound that is ultimately present in the catalyst. That is, using a compound that does not belong to either the CdCl 2 type or the CdI 2 type crystal structure, in the middle of the preparation of the catalyst, the compound and the halogen-containing compound or the hydroxyl group-containing compound are subjected to a contact reaction to finally obtain It may also be an ion-binding compound in the catalyst used.
• magnesium compounds having reducing ability include organomagnesium compounds represented by the following formula.
• nMgR2 -n (Wherein, n is 0 ⁇ n ⁇ 2, and R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 21 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. , two R may be the same or different when n is 0.
• organomagnesium compounds having such reducing ability include dialkyl magnesium such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, octylbutylmagnesium, and ethylbutylmagnesium.
• alkylmagnesium halides such as ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride and amylmagnesium chloride
• alkylmagnesium alkoxides such as butylethoxymagnesium, ethylbutoxymagnesium and octylbutoxymagnesium
• Examples include alkylmagnesium hydride such as propylmagnesium hydride and butylmagnesium hydride.
• organomagnesium compounds having no reducing ability include alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, octoxymagnesium chloride; phenoxymagnesium chloride, methylphenoxymagnesium chloride.
• alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; allyloxymagnesium such as diphenoxymagnesium and methylphenoxymagnesium; magnesium laurate and magnesium carboxylates such as magnesium stearate.
• magnesium metal, magnesium hydride, etc. can also be used.
• These magnesium compounds having no reducing ability may be compounds derived from the above-described magnesium compounds having reducing ability, or compounds derived during preparation of the catalyst.
• the magnesium compound having reducibility is combined with a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, It may be brought into contact with a halogen-containing compound, or a compound having a hydroxyl group or an active carbon-oxygen bond.
• the magnesium compound having reducing ability and the magnesium compound having no reducing ability form a complex compound or double compound with other organometallic compounds such as aluminum, zinc, boron, beryllium, sodium, and potassium. may be the same or may be a mixture.
• the magnesium compound may be used alone, or two or more of the above compounds may be combined, and the magnesium compound may be used in the form of an alcohol complex or in the form of a solid.
• the magnesium compound having reducibility or the magnesium compound having no reducibility is solid, it is preferable to convert it into an alcohol complex state of the magnesium compound using an alcohol, which will be described later.
• the concentration of the metal halide (especially the magnesium halide) in the ethylene polymerization catalyst-containing liquid is preferably 0.10 to 5.0 mmol/L, more preferably 0.20 to 3.0 mmol/L, More preferably, it is 0.30 to 2.0 mmol/L.
• the concentration of the metal halide (especially magnesium halide) used is within the above range, it tends to be possible to easily obtain ethylene-based polymer particles having a specific surface area within the above range.
• alcohols having 1 to 25 carbon atoms examples include alcohols having 1 to 25 carbon atoms. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, 2-butyloctanol, 2-hexyldecanol, 2-hexyldodecanol, 2- Alcohols with 1 to 25 carbon atoms such as octyldecanol, 2-octyldodecanol, isohexadecanol, isoeicosanol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isobutyl alcohol and isopropylbenzyl alcohol Halogen-containing alcohols having 1 to 25 carbon atoms such as trichloromethanol, t
• These alcohols can be used singly or in combination of two or more. Among these, it is preferable to mix and use two types of alcohol from the following viewpoints.
• the two types of alcohols are classified by focusing on the difference in reactivity between the alcohol complex of the metal halide containing the alcohol and the organoaluminum compound and/or the organoaluminum oxy compound described below. The reason why it is preferable to use such two alcohols in combination is speculated as follows.
• An alcohol complex of a metal halide obtained from an alcohol highly reactive with an organoaluminum compound and/or an organoaluminumoxy compound is converted into an alcohol complex of the metal halide by a contact reaction with the organoaluminum compound and/or an organoaluminumoxy compound.
• the alcohol is abstracted from the complex, and the core portion of the metal halide microparticles can be rapidly formed.
• an alcohol complex of a metal halide obtained from an alcohol having relatively low reactivity with the organoaluminum compound and/or the organoaluminum oxy compound is obtained by forming the core portion of the fine particles, and then forming the metal halide. It is thought that the alcohol is withdrawn from the alcohol complex of the compound, the metal halide precipitates outside the nuclei of the fine particles, and the fine particles (A) are formed.
• the fine particles (A) can be expected to have a narrow particle size distribution even though they have a small diameter, and it is thought that the inclusion of extremely small fine particles, for example, by-products of particles having a size similar to that of the nucleus, will be reduced.
• the ethylene-based polymer particles described later are extremely susceptible to the particle size of the fine particles, if the fine particles (A) are used as a component of the olefin polymerization catalyst-containing liquid according to the present invention, amorphous ethylene-based polymer particles can be obtained. Coalesced particles are less likely to form, and even nano-sized polymers are less likely to foul into reaction tanks or the like.
• the difference in reactivity between the alcohol and the organoaluminum compound and/or the organoaluminum oxy compound is considered to be due to the difference in the molecular structure of the alcohol as shown in (i) to (iv) below. .
• alcohols corresponding to alcohols with a relatively small number of carbon atoms in one embodiment may also be alcohols with a relatively large number of carbon atoms depending on the type of the other alcohol. It is sometimes accredited. Taking 2-ethylhexanol as an example, using 2-octyldodecanol as the other alcohol corresponds to an alcohol with relatively few carbon atoms, and isobutyl alcohol as the other alcohol corresponds to carbon It corresponds to an alcohol with a relatively large number of atoms. Since this method focuses on reactivity, there is no problem even if one type of alcohol falls into any category.
• the difference in the number of carbon atoms between the two types of alcohols is 4 or more, considering the manifestation of the effect from the viewpoint of reactivity.
• Specific alcohol combinations include a combination of an alcohol having 2 to 12 carbon atoms and an alcohol having 13 to 25 carbon atoms, and a combination of two alcohols selected from alcohols having 2 to 12 carbon atoms. combinations, etc.
• the alcohol having 2 to 12 carbon atoms preferably has 2 to 10 carbon atoms, and is selected from ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, and octanol. is particularly preferred.
• the alcohol having 13 to 25 carbon atoms preferably has 15 to 25 carbon atoms, more preferably 16 to 25 carbon atoms, such as 2-hexyldecanol, 2-hexyldodecanol, and 2-octyldecanol.
• 2-octyldodecanol, isohexadecanol, isoeicosanol, octadecyl alcohol and oleyl alcohol are particularly preferred.
• the amount of alcohol to be used is not particularly limited as long as it dissolves the metal halide. .1 to 50 mol, more preferably 0.5 to 30 mol, still more preferably 1 to 20 mol, particularly preferably 2 to 15 mol.
• the ratio of the alcohol having a relatively small number of carbon atoms and the alcohol having a relatively large number of carbon atoms is set so that the metal halide dissolves.
• the amount is %, more preferably 85 mol %.
• hydrocarbon solvent is not particularly limited, but specific examples include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane; Among these, decane, dodecane, toluene, xylene, and chlorobenzene are preferred in terms of solubility and reaction temperature.
• hydrocarbon solvent One type of hydrocarbon solvent may be used, or two or more types may be used.
• the amount of the hydrocarbon solvent to be used is not particularly limited as long as it is an amount that dissolves the metal halide. is 0.1 to 100 mol, more preferably 0.2 to 50 mol, still more preferably 0.3 to 40 mol, particularly preferably 0.5 to 30 mol.
• step (2) the alcohol complex of the metal halide obtained in the step (1) is brought into contact with an organoaluminum compound and/or an organoaluminumoxy compound to precipitate the dissolved metal halide, and the fine particles ( A) is the process for producing, and usually a suspension is obtained.
• the step (2) is preferably carried out under temperature conditions of -50 to 200°C, more preferably -20 to 150°C, and even more preferably 0 to 120°C.
• step (2) when the component obtained in step (1) is brought into contact with the organoaluminum compound and/or the organoaluminum oxy compound, it is preferable to carry out while stirring and mixing.
• the stirring and mixing may be carried out under normal stirring conditions, but it may be necessary to stir and mix at high speed.
• Equipment used for high-speed stirring is not particularly limited as long as it is commercially available as an emulsifier or disperser.
• TK Auto Homo Mixer manufactured by Tokushu Kika Kogyo Co., Ltd.
• batch-type emulsifiers such as National Cooking Mixer (manufactured by Matsushita Electric Industrial Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Pipeline Homo Mixer, TK Homomic Line Flow (manufactured by Tokushu Kika Kogyo Co., Ltd.), Colloid Mill (manufactured by Nippon Seiki Co., Ltd.), Thrasher, Trigonal Wet Mill (manufactured by Mitsui Miike Kakoki Co., Ltd.), Cavitron (manufactured by Eurotech), Fine Flow Mill (manufactured by Taiheiyo Kiko Co., Ltd.) Continuous emulsifiers such as
• Organic aluminum compounds that can be used in the present invention include compounds represented by the following formulas (Al-1), (Al-2) and (Al-3). First, the compound represented by the following formula (Al-1) will be described below.
• R a n AlX 3-n (Al-1) (In formula (Al-1), R a is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3.)
• the hydrocarbon group having 1 to 12 carbon atoms is, for example, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
• Specific examples include a methyl group (Me), an ethyl group (Et), an n-propyl group, an isopropyl group, an isobutyl group (iso-Bu), a pentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, isoprenyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.
• organoaluminum compound represented by the formula (Al-1) include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum.
• alkenyl aluminum such as triisoprenyl aluminum
• dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide
• alkylaluminum sesquihalides such as butylaluminum sesquichloride and ethylaluminum sesquibromide
• alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide
• alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride Hydride is mentioned.
• a compound represented by the following formula (Al-2) can also be used as the organoaluminum compound.
• R a n AlY 3-n (Al-2) (In formula (Al-2), R a is the same substituent as in formula (Al-1) above, and Y is —OR b , —OSiR c 3 , —OAlR d 2 , —NR e 2 , —SiR f 3 or a group represented by -N(R g )AlR h 2 , where n is an integer of 1 to 2, and R b , R c , R d and R h are a methyl group, an ethyl group, and an isopropyl group; , isobutyl group, cyclohexyl group, phenyl group, etc., R e is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R f and R g are methyl group, ethyl group, etc.
• the organoaluminum compound represented by the formula (Al-2) As the organoaluminum compound represented by the formula (Al-2), the following compounds are specifically used. (i) a compound represented by R a n Al(OR b ) 3-n and alkylaluminum alkoxides such as ( ii ) compounds represented by R a n Al(OSiR c 3 ) 3-n Bu) 2 Al(OSiEt 3 ). (iii) Compound Represented by R a n Al(OAlR d 2 ) 3-n Examples of the compound include Et 2 AlOAlEt 2 and (iso-Bu) 2 AlOAl(iso-Bu) 2 .
• organoaluminum compound a compound represented by the following formula (Al-3), which is a complex alkylation product of a group I metal and aluminum, can be used.
• M 1 AlR j 4 (Al-3) (In formula (Al-3), M 1 is a group I metal atom such as Li, Na, or K, and R j is a hydrocarbon group having 1 to 15 carbon atoms.) Specific examples of the organoaluminum compound represented by the formula (Al-3) include LiAl(C 2 H 5 ) 4 and LiAl(C 7 H 15 ) 4 .
• organoaluminum compounds mentioned above trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and diisobutylaluminum hydride are particularly preferred.
• the amount of the organoaluminum compound used is preferably 0.1 to 50 mol, more preferably 0.1 to 50 mol per 1 mol of the metal halide. It is 0.2 to 30 mol, more preferably 0.5 to 20 mol, particularly preferably 1.0 to 10 mol.
• organoaluminumoxy compound is not particularly limited, and conventionally known aluminoxanes (benzene-insoluble organoaluminumoxy compounds exemplified in JP-A-2-78687, and exemplified in JP-A-2021-147437. (including organoaluminum oxy compounds containing boron) can be used.
• organic aluminum oxy compounds examples include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane, and specific examples include the organic aluminum oxy compounds described in JP-A-2021-147437.
• One type of organic aluminum oxy compound may be used, or two or more types may be used.
• aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent.
• Compounds containing adsorbed water or salts containing water of crystallization such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate, etc.
• a method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of (1) and reacting the adsorbed water or water of crystallization with the organoaluminum compound.
• organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
• organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.
• the aluminoxane may contain a small amount of organometallic components.
• the obtained aluminoxane may be redissolved in a solvent or suspended in a poor solvent for aluminoxane.
• organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified above as the organoaluminum compounds. Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.
• organoaluminum compounds as described above are used singly or in combination of two or more.
• Solvents used in the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; , cyclohexane, cyclooctane, methylcyclopentane, etc.; petroleum fractions such as gasoline, kerosene, light oil; or halides of said aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, especially Hydrocarbon solvents such as chlorides and bromides are included. Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred.
• the Al component dissolved in benzene at 60° C. is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms. , preferably insoluble or sparingly soluble in benzene.
• R 21 represents a hydrocarbon group having 1 to 10 carbon atoms; Represents 1-10 hydrocarbon groups.
• the organoaluminumoxy compound containing boron represented by the general formula (III) is obtained by dissolving an alkylboronic acid represented by the following general formula (IV) and an organoaluminum compound in an inert gas atmosphere in an inert solvent. It can be produced by reacting at a temperature of ⁇ 80° C. to room temperature for 1 minute to 24 hours.
• R 22 represents the same group as R 22 in general formula (III).
• alkylboronic acids represented by the general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid and n-hexylboronic acid. acids, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like.
• methylboronic acid n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferred. These are used individually by 1 type or in combination of 2 or more types.
• organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified above as the organoaluminum compounds.
• organoaluminum compound trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used individually by 1 type or in combination of 2 or more types.
• the amount of the organoaluminumoxy compound used in precipitating the dissolved metal halide to produce the fine particles (A) is preferably 0.1 to 50 mol, more preferably 0.1 to 50 mol per 1 mol of the metal halide. It is 0.2 to 30 mol, more preferably 0.5 to 20 mol, particularly preferably 1.0 to 10 mol.
• the fine particles (A) obtained through at least the steps (1) and (2) have an average particle diameter of 1 nm or more and 300 nm or less, preferably 1 nm or more and 250 nm or less, more preferably 1 nm or more and 300 nm or less, as measured by a dynamic light scattering method. is 1 nm or more and 200 nm or less, more preferably 1 nm or more and 150 nm or less, even more preferably 1 nm or more and 100 nm or less, and particularly preferably 1 nm or more and 50 nm or less.
• microscopic particles having such a size are considered as follows.
• the specific surface area of the carrier is increased, so that the distance between active sites during ethylene polymerization generated when the transition metal compound (B) described later is supported becomes longer.
• the distance between the active sites is increased in this way, heat generation around the active sites is reduced, the crystallization temperature of the ethylene polymer produced is lowered, and the lamella thickness is reduced. It is also possible to reduce the entanglement of the polymer molecular chains of the produced ethylene polymer.
• the obtained ethylene polymer particles can easily crush the crystal part during stretching, so that the stretching moldability is enhanced, resulting in a degree of orientation. is expected to increase and high strength will be developed.
• the specific surface area of the carrier increases as described above. It becomes possible to increase the supported amount of the compound, and the olefin polymerization activity per catalyst weight can be increased.
• Step ⁇ ii> is a step of bringing the suspension obtained in the step ⁇ i> into contact with the transition metal compound (B).
• Step ⁇ ii> is preferably carried out under temperature conditions of -50 to 100°C, more preferably 0 to 70°C.
• Transition metal compound (B) As the transition metal compound used in the present invention, a known metallocene compound or a specific organic transition metal complex compound such as a so-called post-metallocene can be used without limitation as long as the intrinsic viscosity of the ethylene polymer particles described later can be achieved. can be done.
• an organic transition metal complex having a so-called phenoxyimine ligand described in JP-A-11-315109 is particularly preferred.
• an organic transition metal complex having the structural formula of the following general formula (II) is mentioned as a preferred embodiment.
• M represents a transition metal atom of Groups 4 and 5 of the periodic table, preferably a transition metal atom of Group 4.
• titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc. are preferred, titanium, zirconium and hafnium are more preferred, and titanium or zirconium is particularly preferred.
• m represents an integer of 1-4, preferably an integer of 2-4, more preferably 2.
• R 1 to R 5 may be the same or different, and are hydrogen atom, halogen atom, halogen-containing group, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, two or more of which may be linked together to form a ring .
• the halogen atoms include fluorine, chlorine, bromine, and iodine.
• the hydrocarbon group may be a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms.
• a hydrogen group is mentioned. Specifically, the number of carbon atoms in a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc.
• Linear or branched alkynyl groups having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms; cyclo Cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms such as propyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and adamantyl group; cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as enyl group, indenyl group and fluorenyl group; , preferably 6 to 20, more preferably 6 to 10 aryl groups; alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl and di-t-butylphenyl; etc.
• the hydrocarbon group may have a hydrogen atom substituted with a halogen.
• a hydrocarbon group having a hydrogen atom substituted with a halogen include a trifluoromethyl group, a pentafluorophenyl group, a chlorophenyl group, and the like.
• halogenated hydrocarbon groups having 1 to 30, preferably 1 to 20, carbon atoms.
• the hydrocarbon group may be substituted with other hydrocarbon groups, and examples of hydrocarbon groups substituted with such hydrocarbon groups include aryl group-substituted alkyl groups such as benzyl group and cumyl group. mentioned.
• the hydrocarbon groups are heterocyclic compound residues; Amino group, imino group, amide group, imido group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group became ammonium salt boron-containing groups such as boranediyl, boranetriyl, and diboranyl; mercapto, thioester, dithioester, alkylthio, arylthio, thioacyl, thioether, thiocyanate, isothianic acid Sulfur-containing groups such as ester group, sulfonester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, sulfenyl group; phosphi
• the heterocyclic compound residue includes residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocycles thereof.
• nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine
• oxygen-containing compounds such as furan and pyran
• sulfur-containing compounds such as thiophene
• heterocycles thereof include groups in which the residue of the formula compound is further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms.
• Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, etc. More specifically, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, and a diethylsilyl group. group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl(pentafluorophenyl)silyl group and the like.
• a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group and the like are preferable, and particularly a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group.
• a dimethylphenylsilyl group is preferred.
• Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.
• Examples of the germanium-containing group or the tin-containing group include groups obtained by substituting silicon in the silicon-containing group with germanium or tin.
• specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, t-butoxy group and the like
• specific examples of the aryloxy group include phenoxy group, 2,6-dimethylphenoxy group, 2,4,6-trimethylphenoxy group and the like
• specific examples of the ester group include: An acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and the like
• specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, p-methoxybenzoyl group and the like
• specific examples of the amino acids include a methoxy group, an ethoxy group, an
• a benzimide group etc.
• the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, a phenylthiocarbonyl group and the like.
• Specific examples of the alkylthio group include a methylthio group and an ethylthio group.
• arylthio group examples include a phenylthio group, a methylphenylthio group, a naphthylthio group
• specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, a phenyl sulfonate group, and the like.
• specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, an N-methyl-p-toluenesulfonamide group, and the like.
• hydrocarbon group examples include, in particular, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group and n-hexyl group.
• Aryl groups preferably having 6 to 20; these aryl groups include halogen atoms, alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.
• a substituted aryl group substituted with 1 to 5 substituents such as radicals or aryloxy groups is preferred.
• R 1 to R 5 are heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups as described above. Examples of these groups are the same as those exemplified in the description of the hydrocarbon group.
• R 1 is a linear or branched hydrocarbon group having 1 to 20 carbon atoms, a C 3 to 20 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 20 carbon atoms, or groups in which at least a portion of these groups are substituted with halogen atoms, and halogen-substituted aromatic hydrocarbon groups It is more preferable to have
• R 6 is an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group from the viewpoints of ethylene polymerization catalyst activity, ability to synthesize high molecular weight ethylene polymers, and resistance to hydrogen during polymerization.
• a substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group, or an aromatic hydrocarbon group is preferable, and a branched hydrocarbon group such as a t-butyl group; a benzyl group, 1-methyl-1- Aryl-substituted alkyl groups such as phenylethyl group, 1-methyl-1,1-diphenylethyl group and 1,1,1-triphenylmethyl group;
• An alicyclic hydrocarbon group having a C6-15 alicyclic or multiple ring structure such as a tetracyclododecyl group is more preferred, and a branched hydrocarbon group is even more preferred.
• n is a number satisfying the valence of M
• X is 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, aluminum containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group, and when n is 2 or more, the plurality of groups represented by X are They may be the same or different, and multiple groups represented by X may combine with each other to form a ring.
• halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, and tin-containing group in X examples thereof include those exemplified in the explanation of R 1 to R 5 above. Among these, halogen atoms and hydrocarbon groups are preferred.
• the transition metal compound represented by the general formula (II) can be produced without limitation by the production method described in JP-A-3-130116.
• the amount of transition metal compound (B) used is preferably 1 to 10000 mol, more preferably 10 to 3000 mol, and even more preferably 50 to 1500 mol per 1 mol of metal halide.
• the step ⁇ iii> is a step of adding a compound (F) containing a molecular skeleton represented by the following general formula (I).
• the compound (F) is the compound (F) described in the ethylene polymer particles [2] described above.
• the step ⁇ iii> is between the step ⁇ i> and the step ⁇ ii>, after the step ⁇ ii>, or between the step ⁇ i> and the step ⁇ ii> and the Performed after step ⁇ ii>.
• step ⁇ iii> may be performed not only once but also twice or more.
• the compound (F) By adding the compound (F) during polymerization instead of adding the compound (F) after polymerization, the compound (F) penetrates into the inside of the polymer particles, and a stretched molded product having excellent stretch moldability and strength is obtained. It is possible to easily obtain a binder having less coarse particles and excellent binding properties. In addition, by using such polymer particles, it tends to be possible to easily produce a formed article having sufficient strength and being able to stand on its own even though it is thin, by a dry process.
• the temperature of the suspension when compound (F) is added is preferably 0 to 80°C, more preferably 0 to 80°C, from the viewpoint of contact efficiency between compound (F) and other components in the ethylene polymerization catalyst-containing liquid. is 20-70°C.
• the time required from step ⁇ iii> to the next step is preferably 0 to 60 minutes, more preferably 0 to 40 minutes, and even more preferably 0 to 20 minutes.
• step ⁇ iii> By performing the next step from step ⁇ iii> within this time, it is possible to proceed to the polymerization stage without impairing the catalytic activity of the ethylene polymerization catalyst-containing liquid.
• the concentration of the compound (F) in the polymerization catalyst-containing liquid is greater than 1 mg/L and 150 mg/L or less.
• concentration of the compound (F) is within the above range, the polymerized ethylene polymer particles have excellent stretching moldability and the content of coarse particles can be reduced, thereby improving the fluidity in the pipe during transfer.
• concentration of the compound (F) is more preferably 2.5 mg/L or more and 100 mg/L or less, and still more preferably 4.0 mg/L or more and 75.0 mg, from the viewpoint that generation of coarse particles can be suppressed. /L or less.
• the olefin polymerization catalyst-containing liquid used in this production method essentially contains the fine particles (A), the transition metal compound (B), and the compound (F).
• fine particles (A) and a transition metal compound (B) are added to the olefin polymerization catalyst-containing liquid. and components other than compound (F) can be optionally used.
• Compounds that can be typically used as the other component include a compound (C) that reacts with the transition metal compound (B) to form an ion pair, and an organoaluminum oxy compound (D). It can be used without particular limitation as long as it does not impair the performance of the liquid containing the catalyst for olefin polymerization containing the fine particles (A), the transition metal compound (B) and the compound (F). Examples of compounds that can be used as the compound (C) and the compound (D) include the same compounds as those described in Patent Document 1 above.
• Step [ ⁇ ]> In the step [ ⁇ ], in the presence of the ethylene polymerization catalyst-containing liquid prepared in the step [ ⁇ ], ethylene is homopolymerized, or ethylene is copolymerized with the other monomer, This is a step of producing ethylene-based polymer particles.
• the polymerization may be batchwise, semi-continuous, or continuous.
• the polymerization may be either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.
• one or more inert hydrocarbon media can be used.
• the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; hydrogen; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and the monomer itself can also be used as a solvent.
• aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene
• alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane
• hydrogen
• the transition metal compound (B) is generally used in an amount of 10 ⁇ 11 to 10 mmol, preferably 10 ⁇ 9 to 1 mmol per liter of reaction volume, as metal atoms in the transition metal compound (B). used in large amounts.
• the molar ratio [(C)/(M)] of compound (C) to all transition metal atoms (M) in transition metal compound (B) is usually 0.01 to 100,000. , preferably in an amount of 0.05 to 50,000.
• the molar ratio [(D)/(M)] of compound (D) to all transition metal atoms (M) in transition metal compound (B) is usually 0.01 to 100,000. , preferably in an amount of 0.05 to 50,000.
• the polymerization temperature in the polymerization is preferably -20 to 150°C.
• the lower limit of the polymerization temperature is more preferably 0°C, more preferably 20°C, particularly preferably 30°C, and the upper limit of the polymerization temperature is more preferably 120°C, still more preferably 100°C, particularly preferably 80°C. be.
• the polymerization pressure in the polymerization is usually normal pressure to 10 MPa, preferably normal pressure to 5 MPa.
• the polymerization may be so-called multistage polymerization, in which the reaction is performed in two or more stages by changing the conditions of the polymerization reaction.
• the molecular weight of the resulting ethylene-based polymer particles can be adjusted by a method of allowing hydrogen to exist in the polymerization system, a method of changing the polymerization temperature or polymerization pressure, and the like.
• the ⁇ -olefin having 3 to 20 carbon atoms to be copolymerized with ethylene is preferably an ⁇ -olefin having 3 to 10 carbon atoms, more preferably a carbon atom. It is an ⁇ -olefin of number 3-8.
• linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene; 4-methyl-1-pentene, 3-methyl-1-pentene, 3 -methyl-1-butene, preferably propylene, 1-butene, 1-hexene, 4-methyl-1-pentene.
• the ⁇ -olefins may be used singly or in combination of two or more.
• the content of ⁇ -olefin that is, the molar ratio of repeating units derived from ⁇ -olefin copolymerized with ethylene to all repeating units is 5 mol% or less, preferably 2 mol% or less, more preferably 0.5 mol% or less. .
• the ethylene-based polymer constituting the ethylene-based polymer particles obtained by the present production method is an ethylene homopolymer
• structural defects due to branching are few, so that the stretch-moldability is excellent and a high-strength stretch-molded product can be obtained.
• a copolymer of ethylene and ⁇ -olefin if the content of ⁇ -olefin is more than the above range, branches derived from the ⁇ -olefin become structural defects and sufficient strength cannot be obtained.
• the ethylene content in the ethylene-based polymer can be measured by known measurement methods such as nuclear magnetic resonance (NMR) spectrum measurement and infrared absorption spectrum measurement.
• ethylene-based polymer particles [3] obtained by this production method have the following characteristics (1).
• Intrinsic viscosity [ ⁇ ] measured at 135°C in decalin solvent is 5 to 50 dl/g
• the intrinsic viscosity [ ⁇ ] is preferably 5 to 50 dl/g, more preferably 7 to 50 dl/g, even more preferably 10 to 45 dl/g, and 15 to 45 dl/g. is particularly preferred, and 20 to 45 dl/g is particularly preferred.
• the intrinsic viscosity [ ⁇ ] of the ethylene-based polymer particles is within the above range, the fluidity of the ethylene-based polymer particles is further improved.
• the ethylene-based polymer having an intrinsic viscosity [ ⁇ ] within the above range usually tends to have an extremely high molecular weight. I can say.
• the ethylene-based polymer particles obtained by this production method preferably further have the following characteristics (2) and (3).
• the specific surface area determined by the BET method from the adsorption/desorption isotherm measured by the nitrogen gas adsorption method is greater than 2.00 m 2 /g and 30.0 m 2 /g or less.
• the stretch moldability particularly the solid-phase stretch moldability, is excellent.
• the ethylene-based polymer particles By subjecting the ethylene-based polymer particles to solid-phase stretching molding, it is possible to obtain stretched moldings with extremely high strength and uniform microporous membranes.
• the acetone extract of the ethylene-based polymer particles contains the compound (F).
• the compound (F) has a weight average molecular weight (Mw) specified by gel permeation chromatography (GPC) of 500 or more and 30. ,000 or less is more preferable.
• Mw weight average molecular weight
• GPC gel permeation chromatography
• the oxyarene skeleton of the compound (F) can be identified by a known analytical method such as nuclear magnetic resonance (NMR) spectroscopy, as described later.
• the content of the compound (F) eluted from the ethylene-based polymer particles is preferably 6 ppm or more and 1,000 ppm with respect to the ethylene-based polymer particles. The following are more preferable.
• the ethylene polymer particles were sieved through a mesh sieve of 1 mm x 1 mm for 10 minutes with an amplitude of 0.5 mm and an interval of 15 seconds. It is more preferably 20% by mass or less.
• the bulk density (B.D.) of the ethylene polymer particles is more preferably 0.01 to 0.20 g/mL.
• the magnesium content of the ethylene polymer particles is the same as the magnesium content at the time of production described above. Corresponds to halide concentration. More preferably, the ethylene polymer particles of the present invention contain 10 to 2,000 ppm of magnesium.
• a stretched molded article can be obtained by stretching the ethylene-based polymer particles [3].
• the ethylene-based polymer particles [3] have good fluidity and therefore good moldability. If the moldability is good, for example, it is possible to obtain a stretch-molded product with very high mechanical strength in solid-phase stretch molding.
• Examples of the stretched molded article and the method for producing the same include the methods described in ⁇ Stretched molded article obtained from ethylene-based polymer particles [2] and method for producing the same>>.
• the ethylene-based polymer particles [3] can be dissolved or mixed in a suitable solvent or plasticizer to prepare a gel-like mixture, and a molded article having high strength can be obtained by using a known gel-spinning technique. .
• Stretched molded articles made of ethylene-based polymer particles [3] tend to have higher strength by using so-called ultra-high molecular weight ethylene-based polymer particles with a high intrinsic viscosity [ ⁇ ]. .
• a solid phase stretched molded article molded by a solid phase stretched molding method is particularly preferable. Since the solid-phase stretch molding method is a method of molding without using a solvent, the molding equipment is relatively simple, and the molding method has little adverse effect on the environment. Therefore, it is considered that providing a stretched molded product by such a method will contribute more to society.
• the ethylene-based polymer particles [3] exhibit extremely high stretching performance when solid-phase stretching molding is performed, so it is possible to obtain high-strength fibers, films, sheets, biomaterials such as bone substitute materials, and the like.
• the ethylene-based polymer particles [3] are also useful for producing microporous membranes.
• the thickness of the microporous membrane varies depending on the application, it is usually 0.1-1000 ⁇ m, preferably 1-500 ⁇ m.
• the thickness of the microporous membrane can be measured with a commercially available film thickness gauge.
• the microporous membrane preferably has pores.
• the porosity of the microporous membrane is preferably 30 to 95%, more preferably 40 to 90%, depending on the application. Such an aspect is preferable from the viewpoint of gas permeability and mechanical strength.
• known conditions can be used without limitation, except that the ethylene-based polymer particles [3] are used.
• it can be produced under the same conditions as those of the solid phase stretch molding method for the stretch molded product according to the first aspect of the present invention.
• the draw ratio is preferably 80 times or more, more preferably 100 times or more, and still more preferably 120 times or more. When the draw ratio is within the above range, it can be said that the draw ratio is sufficiently high.
• the stress during stretching is preferably 30 MPa or less, more preferably 25 MPa or less, even more preferably 23 MPa or less, even more preferably 20 MPa or less, and particularly preferably 16 MPa or less.
• the stretched molded product can be molded at a high draw ratio as described above, it is expected to have a high tensile modulus and tensile strength.
• the tensile elastic modulus of the obtained stretched molded product is preferably 80 GPa or more, more preferably 120 GPa or more, and even more preferably 140 GPa or more.
• the strength of the obtained stretched molded product is preferably 1 GPa or more, more preferably 2 GPa or more, still more preferably 2.5 GPa or more, and particularly preferably 3 GPa or more.
• the method for producing the stretched molded article can be produced in the same manner as the method for producing the stretched molded article according to the second aspect of the present invention described above.
• the binder according to the fourth aspect of the present invention (hereinafter also referred to as “this binder”) includes the above-described ethylene polymer particles [1] to [3] (hereinafter collectively referred to as “ethylene polymer particles [4] ).
• PTFE polytetrafluoroethylene
• PVDF polyvinylidene fluoride
• the ethylene-based polymer particles [4] are preferably ultra-high molecular weight ethylene-based polymer particles.
• the ethylene polymer particles [4] used in the present binder may be of one type or two or more types.
• the content of the ethylene polymer particles [4] in the present binder is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95 to 100% by mass. , and more preferably 100% by mass.
• the content of the ethylene-based polymer particles [4] is within the above range, it is possible to easily produce a molded article that has excellent binding properties and can stand on its own even though it is thin, by a dry method.
• the molded article has excellent binding properties and can stand on its own even when the thickness is small. can be easily manufactured.
• the handleability (fluidity) of the ethylene polymer particles [4] is within the range described in the ethylene polymer particles [1] to [3], the handleability (fluidity) is excellent, so it is used as a binding material. becomes good dispersibility. Therefore, it is possible to easily obtain a compact having excellent uniformity (uniformity of the mixed state, uniformity of dimensions and surface condition of the compact).
• the binding properties are excellent.
• a molded body when producing a molded body by a dry method, it may be produced by pressing the molded body-forming material (eg, electrode composite material).
• the molded body-forming material eg, electrode composite material.
• the intrinsic viscosity [ ⁇ ] is within the above range, a compact that can stand on its own even though it is thin can be easily produced by a dry process.
• the ethylene polymer particles [4] are in a molten state during the pressing, the ethylene polymer particles [4] are unlikely to flow out of the molded article, and the particle shape can be maintained. 4], it is possible to improve the adhesion of the components other than 4] and prevent them from coming off from the molded article.
• the compact is an electrode mixture layer, for example, lithium ions can be stably absorbed and released by using the electrode mixture layer.
• the handling property is excellent, the strength is sufficient, and the thickness is large.
• a compact that is thin but can stand on its own can be easily produced by a dry process.
• the ethylene polymer particles [4] contain a large amount of coarse particles, sufficient fluidity cannot be obtained when transferring the ethylene polymer particles after polymerization, and valves, pumps, strainers, etc. may be clogged.
• the content of the coarse particles is within the above range from the viewpoint of being able to suppress such problems.
• the ethylene polymer particles have excellent transportability in the production and processing processes, so uniform particles can be easily obtained, and even if the thickness is thin, sufficient strength can be obtained.
• a molded body that can stand on its own can be easily produced by a dry method.
• the present binder may contain components other than the ethylene polymer particles [4].
• the other components are not particularly limited, and include conventionally known components. ), nitrocellulose, fluororesin, and rubber particles.
• fluororesin examples include PTFE, PVDF, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), vinylidene fluoride-hexafluoropropylene copolymer, and the like.
• Examples of the rubber particles include styrene-butadiene rubber (SBR) particles and acrylonitrile rubber particles.
• SBR styrene-butadiene rubber
• one type may be used, or two or more types may be used.
• the content of the other components in the binder is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and more preferably 0 to 5% by mass. It is particularly preferable not to contain the other components (the content of the other components in the present binder is particularly preferably 0% by mass).
• the content of the olefin polymer particles other than the ethylene polymer particles [4] in the present binder is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and more preferably is 0 to 5% by mass, and it is particularly preferable that the binder does not contain olefin polymer particles other than the ethylene polymer particles [4] (other than the ethylene polymer particles [4] in the binder is particularly preferably 0% by mass).
• the molded article according to the present invention contains the present binder described above and an inorganic material.
• the binder used in the molded body may be of one type or two or more types.
• the inorganic material used for the molded article may be of one type or two or more types.
• the molded article may contain components other than the binder and the inorganic material, depending on the required physical properties, functions, and the like.
• the shape of the molded article is not particularly limited as long as it has a shape suitable for the application of the molded article, and specific examples include block, plate, sheet, and film shapes.
• the molded body is suitably used for batteries, filters, catalysts, absorbers, and the like.
• the molded body include an electrode mixture layer using an active material as the inorganic material, a purification filter using a purifying agent as the inorganic material, a solid catalyst using a catalyst carrier as the inorganic material, and the inorganic material.
• examples include a moisture removing sheet using a moisture absorbent, and an outgassing removing sheet using an outgassing absorbent as the inorganic material.
• the content of the present binder in the molded article is preferably 50% by mass or less, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 12% by mass.
• the content of the binder is within the above range, it is preferable in terms of achieving both the mechanical strength of the resulting molded article and the properties of the inorganic material.
• Inorganic material examples include, but are not limited to, ceramics, metals, metal oxide materials, silicon materials, and carbon materials.
• the inorganic material is not particularly limited as long as it can be bound by the present binder, but it is usually particles (inorganic particles) with an average particle diameter of preferably 1 to 500 ⁇ m, more preferably 1 to 100 ⁇ m. More preferably, it is 5 to 50 ⁇ m.
• the average particle size is measured by the Coulter Counter method.
• the content of the inorganic material in the molded body is preferably 50% by mass or more, more preferably 80 to 99.9% by mass, still more preferably 88 to 99.5% by mass.
• the content of the inorganic material is within the above range, it is preferable in terms of achieving both the mechanical strength of the resulting molded article and the properties of the inorganic material.
• a preferred form of the molded article is an electrode mixture layer.
• the electrode mixture layer preferably contains the present binder and an active material, and is an electrode mixture layer capable of intercalating and deintercalating lithium ions.
• the electrode mixture layer may be a positive electrode mixture layer used for a positive electrode or a negative electrode mixture layer used for a negative electrode.
• the thickness of the electrode mixture layer is not particularly limited, and may be the same thickness as conventionally known electrode mixture layers, but is preferably 30 to 500 ⁇ m, more preferably 30 to 300 ⁇ m, and still more preferably 30 to 150 ⁇ m. is.
• the electrode mixture layer has such a thickness, it is possible to obtain an electrode mixture layer that can stand on its own without a support.
• the content of the binder in the electrode mixture layer is preferably 0.1 to 30 mass from the viewpoint of compatibility between the physical properties of the electrode mixture layer (eg, electrolyte permeability, tensile strength) and battery performance. %, more preferably 0.5 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 0.5 to 12% by mass.
• the content of the present binder is within the above range, it is possible to easily produce an electrode mixture layer with excellent adhesion to the current collector and binding between active materials by a dry method.
• the amount of the active material in the electrode mixture layer can be increased, a battery with a large capacity can be easily obtained by using the electrode mixture layer.
• Electrode material When the electrode mixture layer is used as a positive electrode, a positive electrode active material is usually used as the active material, and when the electrode mixture layer is used as a negative electrode, a negative electrode active material is usually used as the active material.
• the content of the active material in the electrode mixture layer is preferably 70 to 99.9% by mass, more preferably 80 to 99.5% by mass, even more preferably 85 to 99.5% by mass, particularly preferably 88% by mass. ⁇ 99.0% by mass.
• Positive electrode active material Conventionally known positive electrode active materials can be used as the positive electrode active material, and there is no particular limitation. However, when the electrode mixture layer is used in, for example, a lithium ion secondary battery, a material capable of intercalating and deintercalating lithium ions can be used. There is preferably one, and positive electrode active materials commonly used in lithium ion secondary batteries can be mentioned.
• One type of positive electrode active material may be used, or two or more types may be used.
• An oxide containing lithium (Li) and nickel (Ni) as constituent metal elements examples include oxides containing Li, Ni, and at least one of metal elements other than Li and Ni (eg, transition metal elements and typical metal elements) as constituent metal elements.
• the metal element is included in a proportion equal to or lower than that of Ni in terms of the number of atoms.
• Metal elements other than Li and Ni include, for example, Co, Mn, Al, Cr, Fe, V, Mg, Ca, Na, Ti, Zr, Nb, Mo, W, Cu, Zn, Ga, In, Sn, At least one selected from the group consisting of La and Ce is included.
• the positive electrode active material preferably contains a lithium-containing composite oxide (hereinafter also referred to as "NCM") represented by the following formula (C1).
• NCM lithium-containing composite oxide
• LiNi a Co b Mn c O 2 Formula (C1) [In formula (C1), a, b and c are each independently greater than 0 and less than 1, and the sum of a, b and c is 0.99 to 1.00. ] Specific examples of NCM include LiNi0.33Co0.33Mn0.33O2 , LiNi0.5Co0.3Mn0.2O2 , LiNi0.5Co0.2Mn0.3O2 , LiNi0.6Co0.2Mn0.2O2 , LiNi0.8Co0 .1Mn0.1O _ _ _ _ _ 2 is mentioned.
• the positive electrode active material may contain a lithium-containing composite oxide (hereinafter also referred to as "NCA”) represented by the following formula (C2).
• NCA lithium-containing composite oxide
• LitNi ( 1-xy) CoxAlyO2 Formula ( C2 ) [In the formula (C2), t is 0.95 or more and 1.15 or less, x is 0 or more and 0.3 or less, y is 0.1 or more and 0.2 or less, and x and y is less than 0.5. ]
• a specific example of NCA is LiNi 0.8 Co 0.15 Al 0.05 O 2 .
• Negative electrode active material As the negative electrode active material, conventionally known negative electrode active materials can be used, and there is no particular limitation. However, when the electrode mixture layer is used in, for example, a lithium ion secondary battery, a material capable of intercalating and deintercalating lithium ions can be used. There is preferably one, and negative electrode active materials commonly used in lithium ion secondary batteries can be mentioned.
• One type of negative electrode active material may be used, or two or more types may be used.
• negative electrode active materials include metallic lithium, lithium-containing alloys, metals or alloys that can be alloyed with lithium, oxides that can be doped and undoped with lithium ions, and lithium ions that can be doped and undoped. At least one selected from the group consisting of transition metal nitrides and carbon materials capable of doping and dedoping lithium ions.
• carbon materials capable of doping and dedoping lithium ions are preferable.
• Examples of the carbon material include carbon black, activated carbon, amorphous carbon material, and graphite material.
• the shape of the carbon material may be fibrous, spherical, potato-like, flake-like, etc., preferably spherical.
• the average particle diameter of the carbon material is preferably 5-50 ⁇ m, more preferably 10-30 ⁇ m.
• amorphous carbon material examples include hard carbon, coke, mesocarbon microbeads (MCMB) fired at 1500°C or less, and mesophase pitch carbon fiber (MCF).
• MCMB mesocarbon microbeads
• MCF mesophase pitch carbon fiber
• Examples of the graphite material include artificial graphite and natural graphite.
• the graphite material may contain boron.
• the graphite material may be coated with a metal such as gold, platinum, silver, copper, tin, or amorphous carbon, or may be a mixture of amorphous carbon and graphite.
• Examples of the artificial graphite include graphitized MCMB and graphitized MCF.
• the electrode mixture layer may further contain additives other than the binder and the active material.
• additives examples include conductive aids, thickeners, surfactants, dispersants, wetting agents, and antifoaming agents.
• one type may be used, or two or more types may be used.
• the conductive aid is not particularly limited as long as it is a material other than the active material, and known conductive aids can be used. It is preferably a material that improves the electrical conductivity of the material.
• a conductive aid is preferably used in the positive electrode mixture layer, and a conductive aid is also preferably used in the negative electrode mixture layer when a negative electrode active material other than the carbon material is used as the negative electrode active material.
• a conductive aid may or may not be used.
• One type of conductive aid may be used, or two or more types may be used.
• the conductive aid used in the negative electrode mixture layer may be: Although not particularly limited, carbon materials having conductivity are preferred, and include graphite, carbon black, conductive carbon fibers (eg, carbon nanotubes, carbon nanofibers, carbon fibers), fullerenes, and the like.
• a commercially available product may be used as the carbon black.
• Examples of commercially available carbon black include Toka Black #4300, #4400, #4500, #5500 (manufactured by Tokai Carbon Co., Ltd., Furnace Black), Printex L (manufactured by Degussa, Furnace Black), Raven 7000, 5750, 5250, 5000ULTRA III, 5000ULTRA, Conductex SC ULTRA, Conductex 975ULTRA, PUER BLACK100, 115, 205 (manufactured by Columbian, furnace black), #2350, #2400B, #2600B, #30050B, #3030B, # 3230B, #3350B, # 3400B, #5400B (manufactured by Mitsubishi Chemical Corporation, furnace black), MONARCH1400, 1300, 900, VulcanXC-72R, BlackPearls2000, LITX-50, LITX-200 (manufactured by Cabot, furnace black), Ensaco250G, Ensaco260G, Ensaco3 50G, Super-
• graphite examples include artificial graphite and natural graphite (eg, flake graphite, massive graphite, and earthy graphite).
• the electrode according to the present invention includes the electrode mixture layer and a current collector, and when the electrode is used in, for example, a lithium ion secondary battery, it is preferably an electrode capable of intercalating and deintercalating lithium ions.
• the electrode may be a positive electrode or a negative electrode.
• the electrode is preferably an electrode having the electrode mixture layer on at least the surface of a current collector.
• the electrode mixture layer may be provided on the entire surface of the current collector.
• a part of the body may have an electrode mixture layer.
• the electrode may further include a layer (film) other than the electrode mixture layer and the current collector.
• the current collector When the electrode is used as a positive electrode, the current collector is usually a positive electrode current collector, and when the electrode is used as a negative electrode, the current collector is usually a negative electrode current collector.
• the positive electrode current collector is not particularly limited, and known positive electrode current collectors can be used.
• Examples of materials for the positive electrode current collector include metal materials such as aluminum, aluminum alloys, stainless steel, nickel, titanium, and tantalum; and carbon materials such as carbon cloth and carbon paper.
• aluminum is preferable as the material for the positive electrode current collector from the viewpoint of the balance between high conductivity and cost.
• “aluminum” means pure aluminum or an aluminum alloy.
• Aluminum foil is preferable as the positive electrode current collector.
• the material of the aluminum foil is not particularly limited, and examples thereof include A1085 material and A3003 material.
• the negative electrode current collector is not particularly limited, and known negative electrode current collectors can be used.
• Examples of materials for the negative electrode current collector include metal materials such as copper, nickel, stainless steel, and nickel-plated steel.
• copper is preferable as the material of the negative electrode current collector from the viewpoint of workability, etc.
• copper foil is preferable as the negative electrode current collector.
• the electrode is preferably an electrode obtained by a dry method from the viewpoints of simplification of electrode production, economy, safety, environmental load, and the like.
• the electrodes obtained by the dry method are: Step 1 of dry mixing the present binder and the active material to obtain an electrode composite material; An electrode obtained by an electrode manufacturing method including step 2 of forming an electrode mixture layer from the electrode composite material and step 3 of manufacturing an electrode including the electrode mixture layer and a current collector is preferable.
• Step 1 is a step of dry-mixing the binder and the active material to obtain an electrode composite material, and is a step of dry-mixing the binder and the active material without using a solvent or a dispersion medium.
• step 1 the additive may be further used.
• each raw material component can be dry-mixed in an amount such that the content of each component in the resulting electrode composite material is in the same range as the content of each component in the electrode composite material layer. preferable.
• the dry mixing method is not particularly limited, and various known methods such as a defoaming kneader, a dry ball mill, a dry bead mill, a blade planetary mixer, a container rotating planetary mixer, and a grinder. , a mortar, a homogenizer, a low-frequency resonance acoustic mixer, or the like.
• heat treatment may be performed, for example, in order to soften the present binder.
• the heat treatment is preferably performed at a temperature below which the active material, conductive aid, etc. are not decomposed.
• Step 2 is a step of forming an electrode mixture layer from the electrode composite material, and is preferably a step of forming the electrode composite material into a layer (membrane, film).
• the step 2 is preferably a step of forming an electrode mixture layer so that the thickness of the obtained electrode mixture layer is within the above range, and may include a step of applying pressure to the electrode composite material to shape it. preferable.
• the pressure is preferably applied so that the press density of the resulting electrode mixture layer is 1.0 to 4.0 g/cm 3 .
• the press density of the obtained negative electrode mixture layer is preferably 1.0 to 2.0 g/cm 3 , more preferably 1.3 to 1.8 g/cm 3 .
• the positive electrode mixture layer it is preferable to apply pressure so that the press density of the obtained positive electrode mixture layer is 2.5 to 4.0 g/cm 3 .
• the pressure is preferably applied so that the press density of the obtained electrode mixture layer is within the above range, and the pressure is preferably 0.1 to 100 tons.
• the temperature at which the pressure is applied and molded is preferably 20 to 300°C, more preferably 80 to 200°C, and even more preferably 100 to 200°C.
• the binder is moderately softened and the active material can be effectively bound.
• step 2 after the electrode composite material is molded under pressure, if necessary, a step of heating and drying may be performed. From this point of view, it is preferable to omit the heat drying.
• Examples of the heat drying method include drying with warm air, hot air, and low humidity air; vacuum drying; and drying with infrared (eg, far infrared) irradiation.
• infrared eg, far infrared
• the drying time and drying temperature in the heat drying are not particularly limited, but the drying time is, for example, 1 minute to 24 hours, and the drying temperature is, for example, 80 to 180°C.
• Step 3 is a step of manufacturing an electrode including the electrode mixture layer and a current collector, and is preferably a step of stacking the electrode mixture layer and the current collector to manufacture the electrode.
• the lamination method a method of arranging the electrode mixture layer on a current collector and pressing is preferable.
• the pressing method various known pressing methods such as a roll pressing method and a flat plate pressing method can be appropriately adopted.
• the pressing is preferably performed so that the press density of the electrode mixture layer in the obtained electrode is 1.0 to 4.0 g/cm 3 .
• the press density of the negative electrode mixture layer in the resulting negative electrode is preferably 1.0 to 2.0 g/cm 3 , more preferably 1.3 to 1.8 g/cm 3 . Press as much as possible.
• the press density of the positive electrode mixture layer in the positive electrode to be obtained is 2.5 to 4.0 g/cm 3 .
• the press pressure is preferably 0.1 to 100 tons.
• the pressing temperature at the time of pressing is preferably 20 to 300°C, more preferably 80 to 200°C, still more preferably 100 to 200°C.
• the binder is moderately softened, and the electrode mixture layer and the current collector can be effectively laminated.
• the current collector used in step 3 may be previously subjected to surface processing such as surface roughening treatment and formation of a conductive adhesive layer in order to enhance adhesion with the electrode mixture layer.
• step 3 after the electrode mixture layer is pressed onto the current collector, if necessary, a step of heating and drying may be performed. From this point of view, it is preferable to omit the heat drying.
• Examples of the heat drying method include drying with warm air, hot air, and low humidity air; vacuum drying; and drying with infrared (eg, far infrared) irradiation.
• infrared eg, far infrared
• the drying time and drying temperature in the heat drying are not particularly limited, but the drying time is, for example, 1 minute to 24 hours, and the drying temperature is, for example, 80 to 180°C.
• the step 3 may be performed simultaneously with the step 2, or the step 3 may be performed after the step 2.
• the electrode composite material obtained in step 1 is placed (eg, applied) on a current collector as it is and pressed to form an electrode mixture layer, and the electrode mixture layer and the current collector are formed. You may manufacture the electrode which laminated
• the lithium ion secondary battery according to the present invention is not particularly limited as long as it includes the electrodes and the electrolyte.
• the lithium ion secondary battery may have a separator between the negative electrode and the positive electrode, and may have a case that accommodates the electrodes, the electrolyte, and the like.
• the lithium ion secondary battery includes the electrodes, it has excellent battery characteristics (eg, charge/discharge capacity and battery resistance).
• the lithium-ion secondary battery can be suitably used for portable devices and vehicles.
• At least one of the positive electrode and the negative electrode is an electrode obtained by a dry method, particularly by the method for manufacturing the electrode, in order to improve the battery characteristics of the obtained battery. It is preferably an electrode. That is, one of the positive electrode and the negative electrode of the lithium ion secondary battery may be an electrode manufactured by a wet method or the like.
• the electrolyte is not particularly limited as long as it can serve as a conductor for alkali metal cations such as lithium ions. Further, the properties of the electrolyte are not particularly limited, and may be, for example, a liquid dissolved in a non-aqueous solvent described later, a gel, or a solid.
• One type of electrolyte may be used, or two or more types may be used.
• the electrolyte preferably contains at least one type of lithium salt containing fluorine (hereinafter also referred to as "fluorine-containing lithium salt").
• fluorine-containing lithium salts examples include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium hexafluorotantalate (LiTaF 6 ) and other inorganic acid anion salts; lithium trifluoromethanesulfonate ( LiCF3SO3 ) , lithium bis(trifluoromethanesulfonyl ) imide (Li( CF3SO2 ) 2N ), lithium bis(pentafluoroethanesulfonyl) Examples include organic acid anion salts such as imide (Li(C2F5SO2)2N ) . Among these, LiPF 6 is particularly preferable as the fluorine-containing lithium salt.
• a lithium ion secondary battery may contain an electrolyte that is a fluorine-free lithium salt.
• Lithium salts containing no fluorine include lithium perchlorate (LiClO 4 ), lithium tetrachloride aluminum oxide (LiAlCl 4 ), lithium decachlorodecaborate (Li 2 B 10 Cl 10 ), and the like.
• a lithium-ion secondary battery may contain an electrolytic solution obtained by dissolving one or more of the electrolytes in one or more solvents.
• the electrolytic solution is more preferably a non-aqueous electrolytic solution containing one or more of the electrolytes and one or more non-aqueous solvents.
• the electrolyte may contain conventionally known additives used for improving battery performance, etc., other than the electrolyte and the electrolyte.
• the ratio of the fluorine-containing lithium salt to 100% by mass of the electrolyte in the electrolytic solution is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably 80 to 100% by mass.
• the ratio of LiPF 6 to 100% by mass of the electrolyte in the electrolytic solution is also preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 80 to 100% by mass.
• the concentration of the electrolyte in the electrolytic solution is preferably 0.1-3 mol/L, more preferably 0.5-2 mol/L.
• the concentration of LiPF 6 in the electrolytic solution is preferably 0.1 to 3 mol/L, more preferably 0.5 to 2 mol/L.
• non-aqueous solvent examples include cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates, fluorine-containing chain carbonates, aliphatic carboxylic acid esters, fluorine-containing aliphatic carboxylic acid esters, and ⁇ -lactone. fluorinated ⁇ -lactones, cyclic ethers, fluorinated cyclic ethers, chain ethers, fluorinated chain ethers, nitriles, amides, lactams, nitromethane, nitroethane, sulfolane, trimethyl phosphate, dimethyl sulfoxide, dimethyl sulfoxide phosphate.
• Cyclic carbonates include, for example, ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC).
• fluorine-containing cyclic carbonates examples include fluoroethylene carbonate (FEC).
• chain carbonates examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC) and dipropyl carbonate (DPC). be done.
• DMC dimethyl carbonate
• DEC diethyl carbonate
• EMC ethylmethyl carbonate
• MPC methylpropyl carbonate
• EPC ethylpropyl carbonate
• DPC dipropyl carbonate
• fluorine-containing chain carbonates examples include methyl 2,2,2-trifluoroethyl carbonate.
• aliphatic carboxylic acid esters examples include methyl formate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethylbutyrate, ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, ethyl isobutyrate, trimethyl Ethyl butyrate may be mentioned.
• ⁇ -lactones examples include ⁇ -butyrolactone and ⁇ -valerolactone.
• Cyclic ethers include, for example, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, and 1,4-dioxane.
• chain ethers examples include 1,2-ethoxyethane (DEE), ethoxymethoxyethane (EME), diethyl ether, 1,2-dimethoxyethane, and 1,2-dibutoxyethane.
• nitriles examples include acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, and 3-methoxypropionitrile.
• amides examples include N,N-dimethylformamide.
• lactams examples include N-methylpyrrolidinone, N-methyloxazolidinone, and N,N'-dimethylimidazolidinone.
• the non-aqueous solvent preferably contains at least one selected from the group consisting of cyclic carbonates, fluorine-containing cyclic carbonates, chain carbonates and fluorine-containing chain carbonates.
• the total ratio of cyclic carbonates, fluorine-containing cyclic carbonates, linear carbonates and fluorine-containing linear carbonates in the non-aqueous solvent is preferably 50 to 100% by mass, more preferably 60 to 100% by mass. 100% by mass, more preferably 80 to 100% by mass.
• non-aqueous solvent more preferably contains at least one selected from the group consisting of cyclic carbonates and chain carbonates.
• the total proportion of cyclic carbonates and chain carbonates in the nonaqueous solvent is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably 80 to 100% by mass. be.
• the intrinsic viscosity of the non-aqueous solvent is preferably 10.0 mPa ⁇ s or less at 25°C from the viewpoint that the dissociation of the electrolyte and the mobility of ions can be further improved.
• the proportion of the non-aqueous solvent in the non-aqueous electrolyte is preferably 60% by mass or more, more preferably 70% by mass or more.
• the upper limit of the ratio of the non-aqueous solvent in the non-aqueous electrolyte depends on the content of other components (eg, electrolyte), but is, for example, 99% by mass, preferably 97% by mass, more preferably 90% by mass. be.
• the separator is not particularly limited as long as it electrically insulates the positive electrode and the negative electrode and is permeable to lithium ions.
• Examples of materials for the separator include resins such as polyethylene (PE), polypropylene (PP), polyester, cellulose, and polyamide.
• Examples of the separator include a porous flat plate containing the resin, a non-woven fabric containing the resin, and the like.
• a single-layer or multi-layer porous resin film mainly composed of one or more polyolefin resins is preferable.
• the thickness of the separator is, for example, 5 to 30 ⁇ m.
• the case is not particularly limited, and includes known cases for lithium ion secondary batteries, and specific examples thereof include a case containing a laminate film and a case containing a battery can and a battery can lid.
• Examples of the method for producing a lithium ion secondary battery include known methods for producing a lithium ion secondary battery. and an aging step of subjecting the lithium ion secondary battery precursor to aging treatment to obtain a lithium ion secondary battery.
• the precursor preparation step includes a step of housing the positive electrode and the negative electrode (via a separator as necessary) in a case, and an electrolyte (or electrolytic solution) in the case containing the positive electrode and the negative electrode (separator if necessary). ).
• the lithium ion secondary battery precursor is preferably subjected to a combination of charging and discharging one or more times in an environment of 25 to 70°C.
• the specific surface area, median diameter (D50), angle of repose, spatula angle, intrinsic viscosity [ ⁇ ], bulk density, content of coarse particles (1 mm or more), fluidity, Mg The content, acetone extract, compound (F) content in the polymer, and weight average molecular weight (Mw) of compound (F) were measured according to the following methods.
• the adsorption and desorption isotherms of the ethylene-based polymer particles were measured by a nitrogen gas adsorption method using a high-precision gas adsorption device (LA-950, manufactured by Microtrac Bell Co., Ltd.).
• the specific surface area of the ethylene polymer particles was determined from the adsorption/desorption isotherm.
• degassing was performed using a pretreatment device (BELPREP VAC-II manufactured by Microtrack Bell Co., Ltd.).
• ⁇ Median diameter (D50)> The particle size distribution (volume basis) of the ethylene-based polymer particles was measured by a dry method using a laser diffraction scattering measurement device (manufactured by Horiba, Ltd., LA-950). In the obtained particle size distribution, the particle size at which the cumulative volume is 50% was defined as the median size (D50).
• ⁇ Angle of repose, spatula angle> The repose angle and spatula angle were measured using a powder tester (manufactured by Hosokawa Micron). The angle of repose and the angle of the spatula are indicators of fluidity, and smaller angles indicate higher fluidity.
• ⁇ Intrinsic viscosity [ ⁇ ]> The intrinsic viscosity [ ⁇ ] of the ethylene polymer particles is measured in decalin at a temperature of 135° C. by dissolving the particles in decalin and using a fully automatic viscosity measuring device (manufactured by Rigosha, VMR-053UPC). bottom.
• ⁇ Bulk Density> The bulk density of the ethylene-based polymer particles was measured using a standard bulk specific gravity meter (manufactured by Tsutsui Rikagaku Kikai Co., Ltd., JIS K 6720 for vinyl chloride resin).
• ⁇ Liquidity> Using a funnel (foot inner diameter: 8 mm) of a standard umbrella specific gravity measuring device (manufactured by Tsutsui Rikagaku Kikai Co., Ltd., JIS K-6720 for vinyl chloride resin), 200 mL of ethylene polymer particles are put into the funnel. and dropped from the funnel outlet.
• a standard umbrella specific gravity measuring device manufactured by Tsutsui Rikagaku Kikai Co., Ltd., JIS K-6720 for vinyl chloride resin
• Example 1-1 to 1-7 and Comparative Examples 1-1 to 1-5 the fluidity of the ethylene polymer particles was measured from the point at which the ethylene polymer particles began to come out of the funnel outlet. The time (dropping time) until the total amount of coalesced particles finished coming out of the funnel exit was measured, and the dropping time was used for evaluation. A shorter fall time indicates higher fluidity.
• the presence or absence of clogging of the funnel outlet by the ethylene polymer particles was evaluated.
• the absence of clogging at the funnel outlet indicates higher fluidity.
• ICP-MS inductively coupled plasma mass spectrometry
• ⁇ Acetone extract (identification of compound (F))> 400 ml of acetone was added to 10 g mass parts of the ethylene polymer particles, and the mixture was stirred with a stirrer and refluxed for 4 hours for extraction. The obtained acetone slurry was filtered, and the filtrate was concentrated and analyzed by the 1 H-NMR method using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., ECA500).
• a signal derived from a hydrogen atom bonded to a carbon atom adjacent to an oxygen atom in the following formula (I) is observed at 3 to 4 ppm in deuterated acetonitrile with respect to tetramethylsilane.
• R is a hydrogen atom
• a signal derived from an oxymethylene group is observed at 3.3 to 3.8 ppm.
• R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
• EDGE high speed penetration solvent extraction
• EDGE automatic high speed solvent extraction device
• the resulting test solution is subjected to LC-MS (Acquity UPLC H-Class System/SQ Detector manufactured by Waters) to identify the compound (F) contained in the extract, and to the absolute calibration curve method. Quantitative analysis was carried out using the ethylene polymer particles to measure the content of the compound (F) in the ethylene-based polymer particles.
• Example 1-1 ⁇ Preparation of component (i)> 66.1 g (0.694 mol) of anhydrous magnesium chloride, 246 g of dehydrated decane, and 271 g (2.08 mol) of 2-ethylhexyl alcohol were placed in a 1 L glass vessel equipped with a stirrer and sufficiently purged with nitrogen, and reacted at 145° C. for 4 hours. was carried out to obtain a homogeneous and transparent component (i') of 1.0 mol/L in terms of Mg atom.
• the component (i') was diluted with dehydrated decane to obtain a uniform transparent component (i) of 0.25 mol/L in terms of Mg atom.
• a transition metal compound (B-1) represented by the following formula (B-1) was charged in an amount of 4.3 mmol in terms of Ti atom, and then Adeka Pluronic (registered trademark) L-71 (manufactured by ADEKA Corporation, 5.8 g of 5.8 g of hydrogen and 2.7 NL of hydrogen are charged, and then the polymerization reaction is carried out at 50° C. for 117 minutes while supplying ethylene gas so that the total pressure becomes 0.6 MPaG. did After completion of the polymerization, the product was filtered and washed with decane, washed with hexane, and dried under reduced pressure at 80° C. for 18 hours. The obtained ethylene-based polymer particles had good fluidity. Table 1 shows various measurement results.
• t Bu represents a tert-butyl group.
• Example 1-2 ⁇ Ethylene polymerization> 721 kg of dehydrated decane and 2.7 mol of triisobutylaluminum in terms of Al atoms were charged into a sufficiently nitrogen-substituted reactor with a capacity of 1.6 m 3 equipped with a stirrer. After the temperature was raised to 60° C., 0.86 mol of component (i) was charged in terms of Mg atom and stirred for 15 minutes. After that, the reactor was cooled to 40° C., and ethylene gas was blown in until the internal pressure of the reactor reached 0.1 MPaG.
• Example 1-4 The ethylene-based polymer particles obtained in Comparative Example 2 were pulverized with a crushing and granulating machine (Quick Mill QMY type manufactured by Seishin Enterprise Co., Ltd.). The fluidity of the ethylene-based polymer particles obtained by the crushing treatment was good. Table 1 shows various measurement results.
• Example 1-6 [Ethylene polymerization] 130 L of dehydrated decane and 400 mmol of triisobutylaluminum in terms of Al atoms were charged into a 340 L reactor equipped with a stirrer and sufficiently purged with nitrogen. After the temperature was raised to 60° C., 88 mmol of component (i) was charged in terms of Mg atom and stirred for 15 minutes, and then 3.5 g of TR-701 was charged. After cooling to 40 ° C., 0.11 mmol of transition metal compound (B-2) in terms of Zr atom was charged, and 0.04 NL of hydrogen was charged while supplying ethylene gas, and the total pressure was 0.6 MPaG. The polymerization reaction was carried out at 50° C.
• Example 1-7 [Ethylene polymerization] 130 L of dehydrated decane and 490 mmol of triisobutylaluminum in terms of Al atoms were charged into a 340 L reactor equipped with a stirrer and sufficiently purged with nitrogen. After raising the temperature to 60°C, 101mmol of the component (i) was charged in terms of Mg atom and stirred for 15 minutes. Then, 0.51 mmol of transition metal compound (B-1) in terms of Ti atom was charged, then 0.93 g of L-71 and 0.4 NL of hydrogen were charged, and then the total pressure was adjusted to 0.6 MPaG. A polymerization reaction was carried out at 50° C. for 170 minutes while supplying ethylene gas to .
• Table 1 summarizes the measurement results of the above examples and comparative examples. Table 1 also shows the method for controlling the particle diameter (median diameter).
• the pre-stretched tape-shaped compact is passed between hot plates set at 135°C, and the speed difference between the feed pinch roll (roll speed 0.2 m/min) and the take-up pinch roll (roll speed 0.8 m/min).
• First stretching was performed by Furthermore, the set temperature of the hot plate was changed to 140 ° C., and the molded body obtained by the primary stretching was fed with pinch rolls (roll speed 0.2 m / min) and taken-up pinch rolls (roll speed 0.47 m / min) and subjected to secondary stretching.
• a 450 mm piece of the obtained stretched molded product was cut out and weighed, and the draw ratio was determined by subtracting the weight of the original compressed sheet.
• Example 2-7 ⁇ Ethylene polymerization> 500 ml of dehydrated decane was introduced into a 1 L reactor equipped with a stirrer and a baffle plate, which was sufficiently purged with nitrogen, and then purged with ethylene. After the temperature was raised to 60° C., 1.39 mmol of triisobutylaluminum (calculated as Al atom) was charged, and then 0.44 mmol (calculated as Mg atom) of component (i) was charged and stirred for 15 minutes. Then, 7.50 mg of TR-701 was added as compound (F), which is an antistatic agent, and stirred for 3 minutes.
• a transition metal compound (B-3) represented by the following formula (B-3) in terms of Ti atoms was charged, and 3.75 mL of hydrogen was charged.
• a polymerization reaction was carried out at 50° C. for 46 minutes while supplying ethylene gas so that the pressure was 0.5 MPaG.
• the polymer was filtered and washed with decane, washed with hexane, and dried under reduced pressure at 80° C. for 18 hours.
• the obtained ethylene polymer particles weighed 30.2 g. Table 2 shows various measurement results.
• a transition metal compound (B-4) represented by the following formula (B-4) in terms of Ti atoms was charged, and 3.75 mL of hydrogen was charged.
• a polymerization reaction was carried out at 50° C. for 42 minutes while supplying ethylene gas so that the pressure was 0.3 MPaG.
• the polymer was filtered and washed with decane, washed with hexane, and dried under reduced pressure at 80° C. for 18 hours.
• the obtained ethylene-based polymer particles were 30.7 g. Table 2 shows various measurement results.
• a transition metal compound (B-5) represented by the following formula (B-5) in terms of Ti atoms was charged, and 3.75 mL of hydrogen was charged.
• a polymerization reaction was carried out at 50° C. for 49 minutes while supplying ethylene gas so that the pressure was 0.5 MPaG.
• the polymer was filtered and washed with decane, washed with hexane, and dried under reduced pressure at 80° C. for 18 hours.
• the obtained ethylene-based polymer particles weighed 27.4 g. Table 2 shows various measurement results.
• a transition metal compound (B-6) represented by the following formula (B-6) in terms of Ti atoms was charged, and 3.75 mL of hydrogen was charged.
• a polymerization reaction was carried out at 50° C. for 50 minutes while supplying ethylene gas so that the pressure was 0.5 MPaG.
• the polymer was filtered and washed with decane, washed with hexane, and dried under reduced pressure at 80° C. for 18 hours.
• the obtained ethylene polymer particles weighed 28.5 g. Table 2 shows various measurement results.
• a transition metal compound (B-7) represented by the following formula (B-7) in terms of Zr atoms was added, and the mixture was stirred for 3 minutes.
• a polymerization reaction was carried out at 50° C. for 102 minutes while supplying ethylene gas so that the total pressure was 0.1 MPaG.
• the polymer was filtered and washed with decane, washed with hexane, and dried under reduced pressure at 80° C. for 18 hours.
• the obtained ethylene polymer particles weighed 26.8 g. Table 2 shows various measurement results.
• a transition metal compound (B-8) represented by the following formula (B-8) in terms of Zr atoms was added, and the mixture was stirred for 3 minutes.
• a polymerization reaction was carried out at 50° C. for 135 minutes while supplying ethylene gas so that the total pressure was 0.6 MPaG.
• the polymer was filtered and washed with decane, washed with hexane, and dried under reduced pressure at 80° C. for 18 hours.
• the obtained ethylene polymer particles weighed 26.6 g. Table 2 shows various measurement results.
• a transition metal compound (B-9) represented by the following formula (B-9) in terms of Zr atoms was added, and the mixture was stirred for 3 minutes.
• a polymerization reaction was carried out at 50° C. for 109 minutes while supplying ethylene gas so that the total pressure was 0.2 MPaG.
• the polymer was filtered and washed with decane, washed with hexane, and dried under reduced pressure at 80° C. for 18 hours.
• the obtained ethylene polymer particles weighed 27.6 g. Table 2 shows various measurement results.
• a transition metal compound (B-10) represented by the following formula (B-10) in terms of Zr atoms was added, and the mixture was stirred for 3 minutes.
• a polymerization reaction was carried out at 50° C. for 135 minutes while supplying ethylene gas so that the total pressure was 0.5 MPaG.
• the polymer was filtered and washed with decane, washed with hexane, and dried under reduced pressure at 80° C. for 18 hours.
• the obtained ethylene polymer particles weighed 28.0 g. Table 2 shows various measurement results.
• Example 2-16 ⁇ Ethylene polymerization> 500 ml of dehydrated decane was charged into a 1 L reactor equipped with a stirrer and a baffle which was sufficiently purged with nitrogen. After raising the temperature to 60° C., 1.34 mmol of triisobutylaluminum (calculated as Al atom) was charged, and then 0.335 mmol (calculated as Mg atom) of component (i) was charged and stirred for 15 minutes. Next, 1.88 mg of ADEKA Pluronic (registered trademark) L-31 (manufactured by ADEKA Co., Ltd.) was charged as compound (F), which is an antistatic agent, and stirred for 3 minutes.
• ADEKA Pluronic registered trademark
• Example 2-20 ⁇ Ethylene polymerization> 500 ml of dehydrated decane was charged into a 1 L reactor equipped with a stirrer and a baffle which was sufficiently purged with nitrogen. After raising the temperature to 60° C., 1.34 mmol of triisobutylaluminum (calculated as Al atom) was charged, and then 0.335 mmol (calculated as Mg atom) of component (i) was charged and stirred for 15 minutes. Next, 7.50 mg of ADEKA Pluronic 17-R2 (manufactured by ADEKA Co., Ltd.) was charged as compound (F), which is an antistatic agent, and stirred for 3 minutes.
• ADEKA Pluronic 17-R2 manufactured by ADEKA Co., Ltd.
• Example 2-23 ⁇ Ethylene polymerization> 500 ml of dehydrated decane was charged into a 1 L reactor equipped with a stirrer and a baffle which was sufficiently purged with nitrogen. After raising the temperature to 60° C., 1.34 mmol of triisobutylaluminum (calculated as Al atom) was charged, and then 0.335 mmol (calculated as Mg atom) of component (i) was charged and stirred for 15 minutes. Next, 3.75 mg of Emulgen 108 (manufactured by Kao Corporation) was charged as compound (F), which is an antistatic agent, and stirred for 3 minutes.
• Emulgen 108 manufactured by Kao Corporation
• Example 2-26 ⁇ Ethylene polymerization> 500 ml of dehydrated decane was charged into a 1 L reactor equipped with a stirrer and a baffle which was sufficiently purged with nitrogen. After raising the temperature to 60° C., 1.34 mmol of triisobutylaluminum (calculated as Al atom) was charged, and then 0.335 mmol (calculated as Mg atom) of component (i) was charged and stirred for 15 minutes. Next, 6.00 mg of acetylenol E13T (manufactured by Kawaken Fine Chemicals Co., Ltd.) was charged as compound (F), which is an antistatic agent, and stirred for 3 minutes.
• Example 3-1 Ethylene polymerization was carried out in the same manner as in [Example 2-1]. After the polymerization was completed, no adhesion of the polymer was confirmed on the walls of the polymerization vessel (no fouling occurred). Table 3 shows various measurement results.
• Example 3-2 Ethylene polymerization was carried out in the same manner as in [Example 2-2]. After the polymerization was completed, no adhesion of the polymer was confirmed on the walls of the polymerization vessel (no fouling occurred). Table 3 shows various measurement results.
• Example 3-3 Ethylene polymerization was carried out in the same manner as in [Example 2-3]. After the polymerization was completed, no adhesion of the polymer was confirmed on the walls of the polymerization vessel (no fouling occurred). Table 3 shows various measurement results.
• Example 3-4 Ethylene polymerization was carried out in the same manner as in [Example 2-4]. After the polymerization was completed, no adhesion of the polymer was confirmed on the walls of the polymerization vessel (no fouling occurred). Table 3 shows various measurement results.
• Example 3-6 Ethylene polymerization was carried out in the same manner as in [Example 2-7]. After the polymerization was completed, no adhesion of the polymer was confirmed on the walls of the polymerization vessel (no fouling occurred). Table 3 shows various measurement results.
• Example 3-7 Ethylene polymerization was carried out in the same manner as in [Example 2-8]. After the polymerization was completed, no adhesion of the polymer was confirmed on the walls of the polymerization vessel (no fouling occurred). Table 3 shows various measurement results.
• Example 3-8 Ethylene polymerization was carried out in the same manner as in [Example 2-9]. After the polymerization was completed, no adhesion of the polymer was confirmed on the walls of the polymerization vessel (no fouling occurred). Table 3 shows various measurement results.
• Example 3-16 Ethylene polymerization was carried out in the same manner as in [Example 2-17]. After the polymerization was completed, no adhesion of the polymer was confirmed on the walls of the polymerization vessel (no fouling occurred). Table 3 shows various measurement results.
• G The shape of the molded body (film shape) did not change when one end of the molded body was held by hand, and the shape of the molded body was retained (the binder had excellent binding properties).
• P When one end of the molded body was held by hand, the molded body collapsed because the graphite particles were not bonded, or the molded body could not maintain its shape due to breakage or cracking just by holding it by hand. (the binder did not have sufficient binding properties)
• ⁇ Tensile breaking strength of compact> A test piece was prepared by cutting the compact obtained below so that the width in the rolling direction was 5 mm. Using the prepared test piece, using a tensile tester (manufactured by Instron, model 5982 universal testing machine), temperature: 23 ° C., chuck distance: 10 mm, tensile speed: 1 mm / min. The tensile breaking strength in the rolling direction was measured.
• Example 4-1 4 parts by mass of the ethylene polymer particles obtained in Example 1-2 (corresponding to the ethylene polymer particles obtained in Example 2-1 or Example 3-1) as a binder, and natural graphite particles 96 parts by mass were stirred for 5 minutes using a rotation-revolution defoaming mixer (ARE-310, manufactured by Thinky Co., Ltd.) to obtain a mixture.
• ARE-310 rotation-revolution defoaming mixer
• the resulting mixture is filled into a mold (thickness: 0.3 mm, size: 65 mm x 65 mm) and pressed for 3 minutes at a temperature of 23 ° C. using a hydraulic press to perform powder compaction. to obtain a green compact sheet.
• the powder compact sheet is roll-formed using a heating roll press (manufactured by Thank Metal Co., Ltd., roll diameter: 250 mm ⁇ , roll temperature: 200 ° C., roll speed: 0.3 m / min, gap: 100 ⁇ m). was carried out to prepare a film-like molding having a thickness of 100 ⁇ m.
• a heating roll press manufactured by Thank Metal Co., Ltd., roll diameter: 250 mm ⁇ , roll temperature: 200 ° C., roll speed: 0.3 m / min, gap: 100 ⁇ m.
• the self-sustainability evaluation of the obtained molded body was G, and when one end of the molded body was held by hand, the shape of the molded body could be maintained and it was able to stand on its own.
• Example 4-1 A molded article was produced in the same manner as in Example 4-1, except that the ethylene polymer particles (CA-1) were used as the binder instead of the ethylene polymer particles used in Example 4-1. , made an evaluation.
• the physical properties of the ethylene polymer particles (CA-1) were as follows.

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