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WO2020241620A1 - Complexe d'aérogel - Google Patents

Complexe d'aérogel Download PDF

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Publication number
WO2020241620A1
WO2020241620A1 PCT/JP2020/020679 JP2020020679W WO2020241620A1 WO 2020241620 A1 WO2020241620 A1 WO 2020241620A1 JP 2020020679 W JP2020020679 W JP 2020020679W WO 2020241620 A1 WO2020241620 A1 WO 2020241620A1
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WIPO (PCT)
Prior art keywords
airgel
silane compound
resin substrate
sol
acid
Prior art date
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Ceased
Application number
PCT/JP2020/020679
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English (en)
Japanese (ja)
Inventor
昇 川瀬
正洋 山地
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Tiem Factory Inc
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Tiem Factory Inc
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Filing date
Publication date
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Publication of WO2020241620A1 publication Critical patent/WO2020241620A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/02—Polysilicates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials

Definitions

  • the present invention relates to a novel airgel composite, and more particularly to an airgel composite used as a heat insulating material for construction such as a heat insulating window material for a house, a cryogenic container, and a high temperature container.
  • Patent Document 1 a gel-dried product having a siloxane bond called airgel is known (Patent Document 1). Specifically, a sol was formed by hydrolyzing a monomer solution of a silane compound (solvent: water and / or an organic solvent), and a gel (condensation compound) was formed by subjecting the sol to a condensation reaction. After that, the gel is dried to obtain an aerogel (gel dried sol) having a large number of pores.
  • solvent water and / or an organic solvent
  • the pores of the airgel have a pore diameter equal to or smaller than, for example, the mean free path (Mean Free Path [MFP]) of the element molecules constituting the air at atmospheric pressure. Therefore, heat exchange with air is hardly performed inside the airgel, and the airgel has an excellent potential as a heat insulating material, and its heat insulating effect is said to exceed the vacuum.
  • MFP mean Free Path
  • an airgel composite is formed by combining an airgel with a material made of another glass non-woven fabric or a metal sheet to form a sheet, which overcomes brittleness and further suppresses the airgel from falling off from other materials. Proposed.
  • Patent Document 2 improves the handleability to some extent, it still lacks flexibility as a sheet-like material. Therefore, when the airgel composite is applied to a curved surface, the airgel constitutes the airgel composite. The problem of falling off from other materials (for example, powder falling off) has not been sufficiently solved.
  • An object of the present invention is to provide an airgel composite in which airgel shedding is suppressed even when applied to a curved surface.
  • An object of the present invention has been achieved by: 1.
  • An aerogel complex composed of at least a porous resin substrate and an airgel, the airgel is composed of a hydrolyzed condensate of a silane compound, and the silane compound is a tetrafunctional silane compound, a trifunctional silane compound and a bifunctional silane compound.
  • an airgel composite having excellent heat insulating properties, a large area (for example, 400 cm 2 or more) and excellent flexibility in the form of a plate or a film, and a method for producing the same.
  • the airgel composite of the present invention is an airgel composite composed of at least a porous resin substrate and an airgel, and the airgel is composed of a hydrolyzate of a silane compound, and the silane compound is a tetrafunctional silane compound, 3
  • the porous resin substrate is a fibrous resin substrate or a foamed resin substrate.
  • the airgel composite of the present invention may be in a state in which the porous resin substrate and the airgel can be handled as one integrated substance regardless of the production method.
  • a state in which a bond between a functional group on the fiber surface and a functional group on the airgel surface by a chemical interaction, or a bond by an intermolecular interaction between a fiber surface and an airgel encloses a porous resin substrate.
  • the state of adhesion and the like can be mentioned as a preferable embodiment, and particularly preferably, the airgel is present in the pores of the porous resin substrate.
  • the airgel and the porous resin substrate are not easily separated in normal handling, powder dropout is suppressed, and it can be handled as a single integrated substance.
  • the airgel composite of the present invention has flexibility as an airgel composite, it is intended to optimize the silane compound to be mixed in order to produce an airgel, and the production method is not limited.
  • a specific production method for example, there is a case where a sol generation step, a wet gel formation / molding step, a solvent exchange step and a drying step are performed in this order.
  • the size of the airgel composite of the present invention is not particularly limited, but the desired size can be obtained by appropriately selecting the bulk size of the porous resin substrate.
  • the size can be 3000 mm in length, 3000 mm in width, and 100 mm in thickness. It can also be rolled into a width of 2000 mm.
  • the thickness of the airgel layer itself in the airgel composite of the present invention can be appropriately selected, but is 100 ⁇ m to 100 mm, preferably 500 ⁇ m to 40 mm, and more preferably 1 mm to 20 mm.
  • the thickness of the airgel layer can be appropriately selected in relation to the heat insulating property and the powder removing performance of the airgel from the porous resin substrate.
  • the airgel composite can be formed into a sheet or film, but in that case, it can be further combined with another film, sheet or the like. For example, it is preferable to combine it with an aluminum sheet.
  • the airgel composite can be appropriately composited from the viewpoint of handling the porous resin substrate, but it is preferable to appropriately composite the airgel composite in the range of 10 to 1000 parts by mass with respect to 100 parts by mass of the airgel.
  • the porous resin substrate refers to a fibrous resin substrate or a foamed resin substrate, and specifically, a fibrous material, a non-woven fabric, a fiber sheet, felt, a foam, or the like itself maintains a three-dimensional shape. There are things that are done.
  • the porosity is preferably 95% to 99.9% and the density is preferably 0.01 to 0.4 g / cm 3 .
  • Examples of the resin of the porous resin substrate include nylon, polyester, polypropylene, polyacrylonitrile, vinylon, polyolefin, polyurethane, polystyrene, rayon, carbon fiber and the like. Commercially available products can be used as the fibrous resin substrate and the foamed resin substrate of the present invention.
  • the aerogel composite of the present embodiment has, for example, a sol generation step of producing a sol for forming an aerogel, an impregnation step of impregnating a porous resin substrate with the sol obtained in the sol generation step, and gelling the sol.
  • the gel formation step may be performed after the impregnation step, or the impregnation step may be performed after the gel formation step.
  • the porous resin substrate is dispersed in the above sol coating solution in advance, and a porous resin substrate in which airgel is immersed is prepared through an aging step, a washing / solvent replacement step, and a drying step, and this is made into a non-woven fabric. It is also possible to form an airgel composite with a porous resin substrate.
  • the airgel composite and the method for producing the airgel composite in the present invention will be specifically described below.
  • the bifunctional silane compound is a silane compound having two siloxane bonds
  • the trifunctional silane compound is a silane compound having three siloxane bonds
  • 4 The functional silane compound is a silane compound having 4 siloxane bonds.
  • bifunctional silane compound examples include dialkoxysilane and diacetoxysilane.
  • a desirable embodiment of the dialkoxysilane is that the alkoxy group has 1 to 9 carbon atoms. Specific examples thereof include dimethyldimethoxysilane, diethyldimethoxysilane, and diisobutyldimethoxysilane. These compounds may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use dimethyldimethoxysilane (DMDMS) as the bifunctional silane compound.
  • DDMS dimethyldimethoxysilane
  • Examples of the trifunctional silane compound include trialkoxysilane and triacetoxysilane.
  • a desirable embodiment of the trialkoxysilane is that the alkoxy group has 1 to 9 carbon atoms.
  • Examples thereof include silane and octylriethoxysilane. These compounds may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use methyltrimethoxysilane (MTMS) as the trifunctional silane compound.
  • MTMS methyltrimethoxysi
  • tetrafunctional silane compound examples include tetraalkoxysilane and tetraacetoxysilane.
  • a desirable embodiment of the tetraalkoxysilane is that the alkoxy group has 1 to 9 carbon atoms.
  • tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane and the like can be mentioned.
  • These silane compounds may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use tetramethoxysilane (TMS) as the tetrafunctional silane compound.
  • TMS tetramethoxysilane
  • FIG. 1 shows the appropriate range of Qx, Tx and Dx, which are the mass percentages of the tetrafunctional silane compound, the trifunctional silane compound and the bifunctional silane compound, which are the silane compounds of the present invention. It is shown in a triangular diagram having Qx, Tx and Dx as coordinate axes, and the region I shown in FIG. 1 is an appropriate range of Qx, Tx and Dx.
  • Region I shown in FIG. 1 has four vertices a to d and is a trapezoidal segmented region (hatched region with a downward-sloping diagonal line). Since none of the vertices a to d is included in the region I, they are indicated by " ⁇ (white circles)". Further, the straight line connecting the apex a and the vertex b and the straight line connecting the apex b and the apex c are included in the region I, and the straight line connecting the apex c and the apex d and between the apex d and the apex a. The straight line connecting the above is not included in the region I.
  • the mass percentages of the tetrafunctional silane compound, the trifunctional silane compound and the bifunctional silane compound are Qx, Tx and Dx, respectively, with Qx, Tx and Dx as coordinate axes.
  • Qx, Tx, Dx When plotting on the triangular diagram (Qx, Tx, Dx), point A (5,95,0), point B (40,60,0), point C (40,55,5), and D Six straight lines connecting points (30, 55, 15), E points (15, 70, 15), F points (5, 90, 5), and A points (5, 95, 0) in this order. It is preferable that it is within the range surrounded by (region II in FIG. 1) from the viewpoint of heat insulating properties.
  • the region II shown in FIG. 1 has six vertices A to F and is a region partitioned in a hexagonal shape (a region hatched by a diagonal line rising to the right). Since all of the vertices A to F are included in the region II, they are indicated by “ ⁇ (black circle)”, and six straight lines connecting these vertices A to F are also included in the region II.
  • the sol for producing the airgel of the airgel composite of the present invention is a raw material containing a silane compound (main raw material) in a predetermined solution. Is added, and the mixture is produced in a step including a sol forming step of stirring and mixing.
  • a bifunctional silane compound, a trifunctional silane compound, and in some cases a tetrafunctional silane compound are mixed at the above-mentioned predetermined mixing ratio as a main raw material. Then, prepare a solution containing water and a surfactant. By this preparation, the silane compound is hydrolyzed to produce a sol containing a siloxane bond.
  • the solution to be prepared may contain an acid and / or an organic solvent.
  • the surfactant contributes to the formation of the bulk portion and the pore portion constituting the airgel described later in the gel formation process described later.
  • a nonionic surfactant, an ionic surfactant and the like can be used as the surfactant that can be used in the production of airgel.
  • the ionic surfactant include a cationic surfactant, an anionic surfactant, and a zwitterionic surfactant.
  • nonionic surfactants can be preferably used.
  • the amount of the surfactant added to the prepared solution depends on the type and mixing ratio of the silane compound and the type of the surfactant, but is 0.001 to 100% by mass with respect to 100 parts by mass of the total amount of the silane compound as the main raw material. It can be used in the range of parts, preferably in the range of 0.01 to 90 parts by mass, and more preferably in the range of 0.1 to 80 parts by mass.
  • the acid acts as a catalyst during hydrolysis and can accelerate the reaction rate of hydrolysis.
  • Specific examples of acids include inorganic acids, organic acids and organic acid salts.
  • inorganic acid examples include hydrochloric acid, sulfuric acid, sulfite, nitric acid, hydrofluoric acid, phosphoric acid, phosphorous acid, hypochlorous acid, bromic acid, chloric acid, chlorous acid, hypochlorous acid and the like.
  • organic acids examples include carboxylic acids such as acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid, and azelaic acid.
  • carboxylic acids such as acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid, and azelaic acid.
  • organic acid salt acidic aluminum phosphate, acidic magnesium phosphate, acidic zinc phosphate and the like can be used. These acids may be used alone or in combination of two or more. In the present invention, it is preferable to use acetic acid, which is an organic acid, as the acid.
  • a range of 0.0001 mol / L to 0.1 mol / L, particularly a range of 0.0005 mol / L to 0.05 mol / L can be preferably used, and 0.
  • the range of .001 mol / L to 0.01 mol / L can be further preferably used.
  • the organic solvent examples include alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, and t-butanol. These may be used alone or in admixture of two or more. From the viewpoint of compatibility, the amount of the organic solvent added to the prepared solution may be in the range of 4 mol to 10 mol, particularly in the range of 4.5 mol to 9 mol, with respect to the total amount of 1 mol of the silane compound as the main raw material. It is preferably in the range of 5 mol to 8 mol, and is particularly preferable.
  • the solution temperature and time required for the sol formation step depend on the type and amount of the silane compound, surfactant, water, acid, nitrogen compound, organic solvent, etc. in the mixed solution, and are, for example, 0 ° C to 70 ° C.
  • the treatment may be in the range of 0.05 hours to 48 hours under the temperature environment of 20 to 50 ° C., and the treatment is preferably performed for 0.1 hours to 24 hours under the temperature environment of 20 to 50 ° C.
  • the silane compound is hydrolyzed to form a colloid, and a liquid sol can be produced as a whole.
  • auxiliary material and / or the decomposition product of the auxiliary material used in the sol generation step can be mixed as an unavoidable component in the produced airgel.
  • the porous resin substrate of the present invention can be immersed in a sol in this step.
  • the immersion is preferably performed so that the entire porous resin substrate is immersed in the sol. It is also preferable to give vibration so that the sol is immersed even inside the porous resin substrate.
  • the wet gel formation / molding step is a step of adding a basic catalyst to the liquid sol produced in the above-mentioned sol formation step, and a step of pouring a solution to which the basic catalyst is added into a mold for obtaining a desired shape. By curing the solution inside the mold, it can be roughly divided into the steps of producing a wet gel.
  • Examples of the basic catalyst include ammonium compounds such as ammonium hydroxide, ammonium fluoride, ammonium chloride and ammonium bromide, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide, and metaphosphoric acid.
  • ammonium compounds such as ammonium hydroxide, ammonium fluoride, ammonium chloride and ammonium bromide
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide
  • metaphosphoric acid metaphosphoric acid
  • Basic sodium phosphate salts such as sodium, sodium pyrophosphate, sodium polyphosphate, allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, tetramethylethylenediamine, t-butylamine, sec-butylamine, propylamine, 3- (methylamino) propylamine, 3- Aliper amines such as (dimethylamino) propylamine, 3-methoxyamine, dimethylethanolamine, methyldiethanolamine, diethanolamine, triethanolamine, morpholine, N-methylmorpholine, 2-methylmorpholine, piperazine and
  • the basic catalyst may be a nitrogen compound that generates a basic catalyst by heating.
  • the nitrogen compound is added as a compound that generates a basic catalyst during heating in the wet gel formation / molding step.
  • Specific examples thereof include amide compounds such as urea, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and heterocyclic compounds such as hexamethylenetetramine. be able to.
  • urea can be preferably used in the wet gel production step in terms of increasing the production rate.
  • the amount of the basic catalyst added is preferably 0.5 to 5 parts by mass and particularly preferably 1 to 4 parts by mass with respect to 100 parts by mass of the total amount of the main raw material. If the addition amount is less than 0.5 parts by mass, the reaction cannot proceed from the sol to the wet gel, and if it exceeds 5 parts by mass, the reaction is too fast, and the whole may cause non-uniformity inside the mold. ..
  • the aqueous ammonium hydroxide solution is preferable because it has a high reaction promoting effect as a catalyst and can form a reaction from the sol to the wet gel in a short time and with few defects.
  • the aqueous ammonium hydroxide solution is highly volatile, it is also excellent in that it volatilizes in the solvent exchange step and the drying step described later and does not easily remain in the airgel.
  • the amount added in the case of the nitrogen compound is not particularly limited, but for example, the amount of the nitrogen compound added is preferably in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of the silane compound as the main raw material. It is more preferable to use the range of 2 to 150 parts by mass.
  • the porous resin substrate of the present invention can also be immersed in a sol in this step.
  • the step of pouring the solution to which the basic catalyst is added into the mold is a step of obtaining the desired shape of the airgel product.
  • Any of metal, synthetic resin, wood, and paper can be used as the mold, but synthetic resin can be preferably used in that it has both flatness and releasability of the shape.
  • Examples of the synthetic resin include polystyrene, polyethylene, and polypropylene.
  • the mold Since the mold is for obtaining the desired shape of the airgel product, it reflects the shape obtained by reversing the unevenness of the shape of the desired airgel product.
  • the desired shape of the airgel product is a plate shape (rectangular parallelepiped)
  • a concave tray having an opening at one end can be used as a mold.
  • the mold may be a combination mold composed of a plurality of molds, such as a so-called injection molding mold.
  • a combination mold composed of a plurality of molds, such as a so-called injection molding mold.
  • the solution a solution consisting of a sol and a basic catalyst
  • the solution may be poured into a combinatorial interior space and sealed for a predetermined time.
  • a concave tray with an opening at one end When a concave tray with an opening at one end is used as a mold, a flat plate (plate) covering the entire open (flat) surface of the concave tray is prepared as the second mold, and the open surface of the concave tray and the second mold are used. It may be used as a combination type of two sheets so that the two sheets face each other. As a result, the solution (solution consisting of a sol and a basic catalyst) may be poured into the combination type and sealed for a predetermined time.
  • Curing is to proceed the reaction from the sol to the wet gel with a predetermined energy over a predetermined time.
  • energy is heat (temperature), where heating at 30-90 ° C, preferably 40-80 ° C is used.
  • the heating may be heater heating or steam heating with water or an organic solvent.
  • energy application of electromagnetic waves such as infrared rays, ultraviolet rays, microwaves, and gamma rays, application of electron beams, and the like can be mentioned. These energies may be used alone or in combination with a plurality of means.
  • the time required for curing depends on the composition of the silane compound, the type and amount of surfactant, water, acid, nitrogen compound, organic solvent, basic catalyst, etc., and the type and density of energy. The period is between 01 hours and 7 days. When the type of basic catalyst and the type of energy are optimized, gelation may be completed in 0.01 to 24 hours.
  • the curing may be a curing that changes heat (temperature) and time in multiple stages.
  • the material used in the wet gel formation / molding step and / or the decomposition product of the material may be mixed as an unavoidable component in the produced airgel.
  • the solvent exchange step is a step of exchanging water and / or an organic solvent existing on the surface and inside of the wet gel with an organic solvent suitable for short-time drying, but in a subsequent drying step. This is a process that may be omitted if a long time may be required. Further, the solvent exchange step may be performed after being taken out from the above-mentioned mold, or may be performed in the mold.
  • a washing treatment may be performed to wash away the acid used for sol formation, the catalyst used for wet gel formation, the reaction by-product, and the like.
  • An organic solvent can be widely used for the cleaning treatment.
  • Tetrahydrofuran methylene chloride, N, N-dimethylformamide, dimethylsulfoxide, acetic acid, formic acid and various other organic solvents can be used.
  • the above organic solvent may be used alone or in combination of two or more.
  • methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, etc. which are soluble in both water and organic solvents, are used alone or in combination of two or more.
  • the water (or organic solvent) on the surface and inside of the wet gel is replaced with an organic solvent having a surface tension of 45 mN / m or less at 20 ° C. in order to suppress shrinkage damage of the gel in the subsequent drying step.
  • organic solvent having a surface tension of 45 mN / m or less at 20 ° C.
  • examples thereof include dimethyl sulfoxide (43.5 mN / m), cyclohexane (25.2 mN / m), isopropyl alcohol (21 mN / m), heptane (20.2 mN / m), pentane (15.5 mN / m) and the like. ..
  • the organic solvent used in the solvent exchange step has a surface tension at 20 ° C. of 45 mN / m or less, 40 mN / m or less, 35 mN / m or less, 30 mN / m or less, 25 mN / m or less, 20 mN / m or less, 15 mN / m or less. , 5 mN / m or more, 10 mN / m or more, 15 mN / m or more, 20 mN / m or more.
  • an organic solvent containing an aliphatic hydrocarbon whose surface tension at 20 ° C. is in the range of 20 to 40 mN / m.
  • the organic solvent can be used alone or in combination of two or more.
  • the amount of solvent used in the solvent exchange step depends on the temperature at which the solvent is exchanged and the device (container), but it is desirable to use an amount 2 to 100 times the volume of the wet gel.
  • the solvent exchange is not limited to once, and may be performed a plurality of times. Further, the solvent exchange method may be any of total substitution, partial substitution, and cyclic substitution.
  • the type, temperature, and treatment time of the organic solvent may be set independently for each time.
  • the material used in the solvent exchange step and / or the decomposition product of the material may be mixed as an unavoidable component in the produced airgel.
  • the drying step is a step of drying the above-mentioned solvent-exchanged wet gel to obtain an airgel having predetermined properties.
  • the drying method is not particularly limited, the supercritical drying method has problems that the equipment becomes large, the manufacturing cost is extremely high, and mass production is difficult. Therefore, the supercritical drying method of the present invention is supercritical. It is preferable to use the atmospheric pressure drying method without applying the critical drying method.
  • the atmospheric pressure refers to the surface pressure of 300 hPa to 1100 hPa, and as long as it is on the surface of the earth, there is no limitation on the altitude at which the present invention is carried out.
  • the present invention also includes drying under reduced pressure to about 300 hPa.
  • the above-mentioned manufacturing method has described a method for manufacturing an airgel composite having a plate (or rectangular parallelepiped) shape or a film shape, but the present invention is not limited to this, and the plate shape is not limited to this.
  • Processing from the airgel composite into a desired shape can be included as an optional step.
  • it can be processed from a plate (or a rectangular parallelepiped) into various shapes such as a rectangular or circular plate or film, a cube, a sphere, a cylinder, a pyramid, or a cone.
  • Known machining such as wire cutting and laser cutting can be used as the processing method.
  • the airgel composite of the present invention may include processing from a rectangular parallelepiped airgel composite into a particulate airgel composite as an optional step.
  • a known crusher such as a jaw crusher, a roll crusher, and a ball mill can be used.
  • the airgel constituting the airgel composite of the present invention has a bulk portion (gel skeleton) filled with solid matter and 3 in the bulk portion when the structure is observed microscopically. It is mainly composed of through holes penetrating in a three-dimensional network, and forms a three-dimensional network as a whole.
  • the three-dimensional network of airgel of the present invention can be judged by observing with a scanning electron microscope, and the diameter of the through hole of the three-dimensional network structure and the cross-sectional area of the gel skeleton are three-dimensional network-like.
  • the central pore diameter of the through pores (pores), the diameter when the cross section of the skeleton is regarded as a circle, the density, and the porosity can be continuously measured and calculated by the mercury injection method.
  • the bulk part is composed of a continuum in which solids form a three-dimensional network by siloxane bonds.
  • the average length of one side when a grid, which is the smallest unit of a network, is approximated by a cube is 2 nm or more and 25 nm or less.
  • the average length of one side is preferably 2 nm or more, 5 nm or more, 7 nm or more, 10 nm or more, and 25 nm or less, 20 nm or less, and 15 nm or less.
  • the pore portion has a tubular shape penetrating the inside of the bulk portion, and the average inner diameter when the pore is approximated by a tube and the inner diameter of the tube is approximated by a circle is 5 nm or more and 100 nm or less.
  • the average inner diameter of the pores is preferably 5 nm or more, 7 nm or more, 10 nm or more, 20 nm or more, 30 nm or more, 50 nm or more, and 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less.
  • the inner diameter of the tube has a dimension equal to or less than the mean free path (MFP) of the element molecules constituting air at atmospheric pressure.
  • MFP mean free path
  • the porosity of the airgel that is, the ratio of the volume of the pores to the total volume of the airgel is 70% or more. As an example of the porosity, it may be 75% or more, 80% or more, 85% or more, 90% or more.
  • the airgel of the present invention may include a structure other than the bulk portion and the pore portion described above as long as it satisfies the physical properties described later.
  • a void different from the above-mentioned pore portion may be included.
  • water, an organic solvent, a surfactant, a catalyst, and decomposition products thereof that remain as unavoidable components in production can be included as long as the physical properties described later are satisfied. Further, as another example, as long as the physical properties described later are satisfied, dust mixed from the manufacturing space or the manufacturing apparatus can be included as an unavoidable component in manufacturing.
  • the airgel composite of the present invention may contain components to be added with the intention of imparting functionality, improving appearance, imparting decorativeness, etc., in addition to the above-mentioned constitution.
  • antistatic agents, lubricants, inorganic pigments, organic pigments, inorganic dyes, and organic dyes can be included. These can be contained in each of the porous resin substrate and the airgel.
  • the airgel of the present invention has a density as low as 0.15 g / cm 3 or less.
  • the density is obtained by the mercury intrusion method.
  • the airgel composite of the present embodiment can be applied to applications as a heat insulating material in a cryogenic container, a space field, a building field, an automobile field, a home appliance field, a semiconductor field, an industrial facility, and the like.
  • the airgel composite material of the present embodiment can be used for water repellency, sound absorption, static vibration, catalyst support, and the like.
  • MTMS methyltrimethoxysilane
  • DDMMS dimethyldimethoxysilane
  • TMOS tetramethoxysilane
  • the wet gel was aged by allowing it to stand for 96 hours in succession.
  • the wet gel was taken out from the closed container, immersed in a MeOH solution corresponding to 5 times the volume of the wet gel, and the solvent was exchanged repeatedly 5 times under the condition of 60 ° C. for 8 hours.
  • Immerse in an IPA / hep mixed solution corresponding to 5 times the volume of the wet gel which is a mixture of isopropyl alcohol (IPA) and heptan (Hep) in a volume ratio of 1: 4 to 1: 3, and 8 at 60 ° C. Further solvent exchange was carried out under time conditions.
  • IPA isopropyl alcohol
  • Hep heptan
  • the mixture was immersed in a Hep solution corresponding to 5 times the volume of the wet gel, and the solvent was exchanged twice under the condition of 60 ° C. for 8 hours.
  • the methanol and isopropanol used for the solvent exchange were both manufactured by Nacalai Tesque.
  • the solvent in the wet gel was placed in a container (dryer) whose evaporation rate could be controlled, and drying was started.
  • the drying temperature was set to be equal to or lower than the boiling point of the solvent, and the solvent evaporation rate of the gel exchanged (replaced) with a low surface tension solvent was adjusted to 0.2 g / (h ⁇ cm 3 ) from immediately after the start of drying to 4 hours. After that, the solvent evaporation rate was gradually reduced, and when the gel mass became constant, drying was completed to prepare a sheet-shaped airgel composite.
  • Other examples were prepared in the same manner.
  • Comparative Examples 1 and 2 were produced in the same manner as in Example 1.
  • Comparative Example 3 the same composition as the airgel composite material described in Example 1 of JP-A-2018-11183 (Patent Document 2) was prepared and used.
  • the airgel composite of the embodiment of the present invention has a small amount of powder falling off.
  • the airgel composite of Comparative Example 3 (described in Example 1 of Patent Document 1) has already fallen off at the stage of preparing a sample, and the amount of powder fallen is clearly larger than that of the example of the present invention. (More than in Comparative Example 2), and even the reproducibility of the test results was problematic, so the results are not shown in Table 1.
  • Example 2 An airgel composite having the composition shown in Table 2 was prepared according to the method for producing an airgel composite of Experimental Example 1, and the same evaluation was performed. Although the absolute amount of powder falling is different from that of Experimental Example 1 due to the difficulty in reproducibility of the experiment, sufficient comparison can be made within the same experiment.
  • the amount of cut powder dropped 7.5 mg or less was judged to be ⁇
  • the amount of bent powder dropped 5.0 mg or less was judged to be ⁇
  • the others were marked with x.
  • the composition having a Dx of more than 30% by mass and the composition not containing Qx had a problem in the progress of the reaction of the airgel itself, and could not be evaluated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Thermal Insulation (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un complexe d'aérogel ayant une perte d'aérogel supprimée, même lorsqu'il est appliqué à une surface courbée. La solution selon l'invention porte sur un complexe d'aérogel comprenant au moins un matériau de base en résine poreuse et un aérogel. L'aérogel comprend un condensat hydrolysé d'un composé silane. Le composé silane satisfait 0 < Qx < 50, 50 ≤ Tx < 100 et 0 ≤ Dx < 30 (où Qx + Tx + Dx = 100) lorsque les pourcentages en masse d'un composé silane tétrafonctionnel, d'un composé silane trifonctionnel et d'un composé silane bifonctionnel sont respectivement Qx, Tx et Dx.
PCT/JP2020/020679 2019-05-27 2020-05-26 Complexe d'aérogel Ceased WO2020241620A1 (fr)

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JP2019-098683 2019-05-27
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JP2019151348A JP6683870B1 (ja) 2019-05-27 2019-08-21 エアロゲル複合体

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JP7701028B2 (ja) * 2020-04-07 2025-07-01 ティエムファクトリ株式会社 エアロゲルパウダー組成物
JP7576346B2 (ja) * 2021-01-26 2024-10-31 国立研究開発法人物質・材料研究機構 ポリシロキサン多孔体の製造方法、ポリシロキサン多孔体、保温材、及び、保温容器
WO2025204922A1 (fr) * 2024-03-25 2025-10-02 住友理工株式会社 Poudre d'aérogel de silice utilisée pour un matériau d'isolation thermique pour bloc-batterie, et matériau d'isolation thermique pour bloc-batterie

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Cited By (3)

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JP7641340B1 (ja) 2023-09-21 2025-03-06 住友理工株式会社 バッテリーパック用断熱材およびその製造方法
WO2025063173A1 (fr) * 2023-09-21 2025-03-27 住友理工株式会社 Matériau d'isolation thermique pour batteries et son procédé de production
JP2025047292A (ja) * 2023-09-21 2025-04-03 住友理工株式会社 バッテリーパック用断熱材およびその製造方法

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