WO2017038775A1 - エアロゲル - Google Patents
エアロゲル Download PDFInfo
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- WO2017038775A1 WO2017038775A1 PCT/JP2016/075224 JP2016075224W WO2017038775A1 WO 2017038775 A1 WO2017038775 A1 WO 2017038775A1 JP 2016075224 W JP2016075224 W JP 2016075224W WO 2017038775 A1 WO2017038775 A1 WO 2017038775A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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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
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
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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
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/159—Coating or hydrophobisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- 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
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- 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
- C08J9/286—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 the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
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- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/024—Organogel, i.e. a gel containing an organic composition
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- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/028—Xerogel, i.e. an air dried gel
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- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
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- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/06—Flexible foams
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- 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
- C08J2383/00—Characterised by the use 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; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Definitions
- the present invention relates to an airgel excellent in heat insulation and productivity.
- Silica airgel is known as a material having low thermal conductivity and heat insulation. Silica airgel is useful as a functional material having excellent functionality (thermal insulation, etc.), unique optical properties, and unique electrical properties. For example, an electronic substrate utilizing the ultra-low dielectric constant properties of silica airgel It is used as a material, a heat insulating material using the high heat insulating property of silica airgel, a light reflecting material using the ultra-low refractive index of silica airgel, and the like.
- a supercritical drying method in which a gel-like compound (alcogel) obtained by hydrolyzing and polymerizing alkoxysilane is dried under supercritical conditions of a dispersion medium.
- an alcogel and a dispersion medium solvent used for drying
- the dispersion medium is applied to the supercritical fluid by applying a temperature and pressure above its critical point to form a supercritical fluid. It is a method of removing the solvent.
- the supercritical drying method requires a high-pressure process, capital investment is required for a special apparatus that can withstand supercriticality, and much labor and time are required.
- the obtained airgel is poor in handling and large in size. Because it was difficult, there was a problem in productivity. For example, the agglomerated airgel obtained by the above process may be broken simply by trying to lift it by hand. This is presumably due to the fact that the density of the airgel is low and that the airgel has a pore structure in which fine particles of about 10 nm are weakly connected.
- This invention is made
- the present inventor has exhibited excellent heat insulating properties when an airgel is produced by using a polysiloxane compound having a molecular weight in a specific range, and handles it. Therefore, it has been found that productivity can be increased because the productivity is improved and the size can be increased, and the present invention has been completed.
- the present invention relates to a hydrolysis of a polysiloxane compound having a hydrolyzable functional group or a condensable functional group and having an average molecular weight of 300 to 1500 g / mol, and a polysiloxane compound having a hydrolyzable functional group
- An airgel that is a dried product of a wet gel that is a condensate of a sol containing at least one selected from the group consisting of products is provided.
- the airgel obtained in this way is excellent in heat insulation and productivity.
- the airgel of the present invention can have a structure represented by the following general formula (1).
- Such an airgel is excellent in heat insulation and productivity.
- R 1 and R 2 each independently represent an alkyl group or an aryl group
- R 3 and R 4 each independently represent an alkylene group.
- the airgel of the present invention can have a structure represented by the following general formula (1a) as a structure including the structure represented by the general formula (1).
- R 1 and R 2 each independently represents an alkyl group or an aryl group
- R 3 and R 4 each independently represent an alkylene group
- p represents an integer of 3 to 15.
- the airgel of this invention has a ladder type structure provided with a support
- Such an airgel has excellent flexibility resulting from the ladder structure while maintaining the heat insulating property of the airgel itself.
- R 5 and R 6 each independently represents an alkyl group or an aryl group, and b represents an integer of 3 to 15.
- Examples of the airgel having a ladder structure include those having a ladder structure represented by the following general formula (3). Thereby, more excellent heat insulation and flexibility can be achieved.
- R 5 , R 6 , R 7 and R 8 each independently represents an alkyl group or an aryl group, a and c each independently represent an integer of 1 to 3000, and b is 3 to 15 Indicates an integer.
- Examples of the condensable functional group include a hydroxyalkyl group, and the hydroxyalkyl group can have 1 to 6 carbon atoms. Thereby, it becomes the airgel which has the more excellent heat insulation and a softness
- examples of the polysiloxane compound include those represented by the following general formula (A). Thereby, more excellent heat insulation and flexibility can be achieved.
- R 1a represents a hydroxyalkyl group
- R 2a represents an alkylene group
- R 3a and R 4a each independently represents an alkyl group or an aryl group
- n represents an integer of 3 to 15.
- examples of the hydrolyzable functional group include an alkoxy group, and the alkoxy group may have 1 to 6 carbon atoms. Thereby, it becomes the airgel which has the more excellent heat insulation and a softness
- examples of the polysiloxane compound include those represented by the following general formula (B). Thereby, more excellent heat insulation and flexibility can be achieved.
- R 1b represents an alkyl group, an alkoxy group or an aryl group
- R 2b and R 3b each independently represent an alkoxy group
- R 4b and R 5b each independently represent an alkyl group or an aryl group
- M represents an integer of 3 to 15.
- the sol is composed of a hydrolyzable functional group or a silicon compound having a condensable functional group (excluding a polysiloxane compound) and a hydrolysis product of the silicon compound having a hydrolyzable functional group. It may further contain at least one selected from the group consisting of: Thereby, the further outstanding heat insulation and productivity can be achieved.
- the dried product can be obtained by drying performed at a temperature below the critical point of the solvent used for drying the wet gel and at atmospheric pressure. Thereby, it becomes easier to obtain an airgel excellent in heat insulation and productivity.
- an airgel excellent in heat insulation and productivity can be provided.
- a polysiloxane compound having a molecular weight in a specific range when an airgel is produced, excellent heat insulation is expressed, handling is improved, and the size can be increased, thereby increasing productivity. it can.
- a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value of a numerical range in a certain step may be replaced with the upper limit value or the lower limit value of a numerical range in another step.
- the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
- “A or B” only needs to include either A or B, and may include both.
- the materials exemplified in the present specification can be used singly or in combination of two or more unless otherwise specified.
- the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. means.
- the obtained low-density dried gel is referred to as “aerogel” regardless of the drying method of the wet gel.
- the airgel means “a gel composed of a microporous solid whose dispersed phase is a gas”, which is an aerogel in a broad sense, that is, “Gel compressed of a microporous solid in which the dispersed phase is a gas”. To do.
- the inside of an airgel has a network-like fine structure, and has a cluster structure in which airgel particles of about 2 to 20 nm (particles constituting the airgel) are bonded. There are pores less than 100 nm between the skeletons formed by these clusters. Thereby, the airgel has a three-dimensionally fine porous structure.
- the airgel in this embodiment is a silica airgel which has a silica as a main component, for example.
- the silica airgel include so-called organic-inorganic hybrid silica airgel into which an organic group (such as a methyl group) or an organic chain is introduced.
- the airgel of this embodiment is excellent in heat insulation and productivity (flexibility).
- the airgel of this embodiment includes a polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and an average molecular weight of 300 to 1500 g / mol, and a hydrolyzable functional group
- a wet gel dried product (the above sol) which is a condensate of a sol containing at least one selected from the group consisting of hydrolysis products of polysiloxane compounds having the following (hereinafter sometimes referred to as “polysiloxane compound group”) Obtained by drying a wet gel produced from By setting the average molecular weight of the polysiloxane compound within this range, an airgel excellent in heat insulation and productivity can be obtained.
- the hydrolyzable functional group and the condensable functional group in the polysiloxane compound are not particularly limited.
- the hydrolyzable functional group include an alkoxy group.
- Examples of condensable functional groups include hydroxyl groups, silanol groups, carboxyl groups, phenolic hydroxyl groups, and the like.
- the hydroxyl group may be contained in a hydroxyl group-containing group such as a hydroxyalkyl group.
- a polysiloxane compound having a hydrolyzable functional group or a condensable functional group is a reactive group (hydrolyzable functional group and condensable functional group) different from the hydrolyzable functional group and the condensable functional group.
- the reactive group include an epoxy group, a mercapto group, a glycidoxy group, a vinyl group, an acryloyl group, a methacryloyl group, and an amino group.
- the epoxy group may be contained in an epoxy group-containing group such as a glycidoxy group.
- These polysiloxane compounds having functional groups and reactive groups may be used alone or in admixture of two or more.
- the alkoxy group, silanol group, and hydroxyalkyl group can further improve the flexibility of the airgel, and the alkoxy group and hydroxyalkyl group further improve the compatibility of the sol. can do.
- the number of carbon atoms of the alkoxy group and hydroxyalkyl group can be 1 to 6, but the flexibility of the airgel is further improved. From the viewpoint, it may be further 2-4.
- the average molecular weight of the polysiloxane compound can be 300 g / mol or more from the viewpoint of further improving the flexibility of the airgel, but may be 500 g / mol or more.
- it can be 1500 g / mol or less, but may be 1200 g / mol or less. That is, the average molecular weight of the polysiloxane compound can be 300 to 1500 g / mol, but may be 500 to 1200 g / mol.
- the average molecular weight can be measured by an average molecular weight (Mw) calculated in terms of polystyrene using GPC (gel permeation chromatography). Specifically, it can be detected by RI (differential refraction detector) using toluene eluent.
- Mw average molecular weight
- Examples of the polysiloxane compound having a hydroxyalkyl group include those having a structure represented by the following general formula (A).
- R 1a represents a hydroxyalkyl group
- R 2a represents an alkylene group
- R 3a and R 4a each independently represents an alkyl group or an aryl group
- n represents an integer of 3 to 15.
- examples of the aryl group include a phenyl group and a substituted phenyl group.
- examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
- two R 1a s may be the same or different, and similarly, two R 2a s may be the same or different.
- two or more R 3a s may be the same or different, and similarly two or more R 4a s may be the same or different.
- R 1a includes a hydroxyalkyl group having 1 to 6 carbon atoms, and examples of the hydroxyalkyl group include a hydroxyethyl group, a hydroxypropyl group, and the like.
- examples of R 2a include an alkylene group having 1 to 6 carbon atoms, and examples of the alkylene group include an ethylene group and a propylene group.
- R 3a and R 4a each independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like, and examples of the alkyl group include a methyl group and the like.
- n can be 3 to 15, but may be 6 to 12.
- polysiloxane compound having the structure represented by the general formula (A) a commercially available product can be used, and compounds such as X-22-160AS, KF-6001, KF-6002, and KF-6003 (all of them) , Manufactured by Shin-Etsu Chemical Co., Ltd.), compounds such as XF42-B0970, Fluid OFOH 702-4% (all manufactured by Momentive).
- Examples of the polysiloxane compound having an alkoxy group include those having a structure represented by the following general formula (B).
- R 1b represents an alkyl group, an alkoxy group or an aryl group
- R 2b and R 3b each independently represent an alkoxy group
- R 4b and R 5b each independently represent an alkyl group or an aryl group.
- M represents an integer of 3 to 15.
- examples of the aryl group include a phenyl group and a substituted phenyl group.
- examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
- two R 1b s may be the same or different from each other, and two R 2b s may be the same or different from each other, and similarly two R 1b s. 3b may be the same or different.
- two or more R 4b may be each independently selected from the same, as well two or more R 5b may also each independently selected from the same.
- R 1b examples include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the like.
- alkyl group or alkoxy group A methyl group, a methoxy group, an ethoxy group, etc. are mentioned.
- R 2b and R 3b each independently include an alkoxy group having 1 to 6 carbon atoms, and examples of the alkoxy group include a methoxy group and an ethoxy group.
- R 4b and R 5b each independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like, and examples of the alkyl group include a methyl group and the like.
- m can be 3 to 15, but may be 6 to 12.
- the polysiloxane compound having the structure represented by the general formula (B) can be obtained by appropriately referring to the production methods reported in, for example, JP-A Nos. 2000-26609 and 2012-233110. Can do.
- the polysiloxane compound having an alkoxy group may exist as a hydrolysis product in the sol, and the polysiloxane compound having an alkoxy group and the hydrolysis product are mixed. You may do it.
- the polysiloxane compound having an alkoxy group all of the alkoxy groups in the molecule may be hydrolyzed or partially hydrolyzed.
- polysiloxane compounds having hydrolyzable functional groups or condensable functional groups and the hydrolysis products of polysiloxane compounds having hydrolyzable functional groups may be used alone or in combination of two or more. May be used.
- the sol containing the polysiloxane compound or the hydrolysis product thereof may contain a silicon compound (silicon compound) other than the polysiloxane compound. That is, the sol of this embodiment includes a hydrolyzable functional group or a silicon compound having a condensable functional group (excluding a polysiloxane compound) and a hydrolysis product of a silicon compound having a hydrolyzable functional group. It may further contain at least one selected from the group consisting of (hereinafter, sometimes referred to as “silicon compound group”). The number of silicon atoms in the molecule of the silicon compound can be 1 or 2.
- the silicon compound having a hydrolyzable functional group is not particularly limited, and examples thereof include alkyl silicon alkoxides. Among alkyl silicon alkoxides, those having 3 or less hydrolyzable functional groups can further improve water resistance. Examples of such alkyl silicon alkoxides include monoalkyltrialkoxysilanes, monoalkyldialkoxysilanes, dialkyldialkoxysilanes, monoalkylmonoalkoxysilanes, dialkylmonoalkoxysilanes, and trialkylmonoalkoxysilanes. Examples thereof include methyltrimethoxysilane, methyldimethoxysilane, dimethyldimethoxysilane, and ethyltrimethoxysilane.
- the silicon compound having a condensable functional group is not particularly limited.
- silane tetraol, methyl silane triol, dimethyl silane diol, phenyl silane triol, phenyl methyl silane diol, diphenyl silane diol, n-propyl silane triol examples include hexyl silane triol, octyl silane triol, decyl silane triol, and trifluoropropyl silane triol.
- the silicon compound having a hydrolyzable functional group or a condensable functional group may further have the above-described reactive group different from the hydrolyzable functional group and the condensable functional group.
- the number of hydrolyzable functional groups is 3 or less, and as a silicon compound having a reactive group, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, N-phenyl-3-amino Propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like can also be used.
- vinylsilane triol 3-glycidoxypropylsilanetriol, 3-glycidoxypropylmethylsilanediol, 3-methacryloxypropylsilanetriol, 3-methacryloxypropylmethylsilanediol, 3-acryloxypropylsilanetriol, 3-mercaptopropylsilanetriol, 3-mercaptopropylmethylsilanediol, N-phenyl-3-aminopropylsilanetriol, N-2- (aminoethyl ) -3-Aminopropylmethylsilanediol and the like can also be used.
- bistrimethoxysilylmethane bistrimethoxysilylethane
- bistrimethoxysilylhexane ethyltrimethoxysilane
- vinyltrimethoxysilane etc.
- hydrolyzable functional groups or condensable functional silicon compounds, and hydrolyzed products of hydrolyzable functional silicon compounds may be used alone or in admixture of two or more. May be.
- the content of the polysiloxane compound group contained in the sol can be 5 parts by mass or more with respect to 100 parts by mass of the sol, and may be 10 parts by mass or more.
- the content can be 50 parts by mass or less, or 30 parts by mass or less with respect to 100 parts by mass of the total amount of sol. That is, the content of the polysiloxane compound group can be 5 to 50 parts by mass with respect to 100 parts by mass of the total amount of the sol, but can also be 10 to 30 parts by mass.
- the content of the polysiloxane compound group and the content of the silicon compound group can be 1: 0.5 to 1: 4, but can also be 1: 1 to It may be 1: 2.
- the ratio of the content of these compounds is 1: 0.5 or more, good compatibility is further easily obtained, and when the ratio is 1: 4 or less, gel shrinkage is further easily suppressed.
- the total content of the polysiloxane compound group and the silicon compound group can be 5 parts by mass or more with respect to 100 parts by mass of the sol, and may be 10 parts by mass or more.
- the total content can be 50 parts by mass or less, or 30 parts by mass or less, with respect to 100 parts by mass of the total amount of sol. That is, the total content of the polysiloxane compound group and the silicon compound group can be 5 to 50 parts by mass with respect to 100 parts by mass of the sol, but may be 10 to 30 parts by mass.
- the ratio of the contents of the polysiloxane compound group and the silicon compound group can be within the above range.
- the airgel of this embodiment includes a polysiloxane compound having a hydrolyzable functional group or a condensable functional group and an average molecular weight of 300 to 1500 g / mol, and a polysiloxane compound having a hydrolyzable functional group
- a dried product of a wet gel which is a condensate of the above sol containing at least one selected from the group consisting of hydrolysis products of (obtained by drying a wet gel generated from the above sol) .
- the condensate may be obtained by a condensation reaction of a hydrolysis product obtained by hydrolysis of a polysiloxane compound having a hydrolyzable functional group, and is not a functional group obtained by hydrolysis.
- the polysiloxane compound only needs to have at least one of a hydrolyzable functional group and a condensable functional group, and may have both a hydrolyzable functional group and a condensable functional group.
- the airgel of the present embodiment can contain a polysiloxane having a main chain including a siloxane bond (Si—O—Si).
- the airgel can have the following M unit, D unit, T unit or Q unit as a structural unit.
- R represents an atom (hydrogen atom or the like) or an atomic group (alkyl group or the like) bonded to a silicon atom.
- the M unit is a unit composed of a monovalent group in which a silicon atom is bonded to one oxygen atom.
- the D unit is a unit composed of a divalent group in which a silicon atom is bonded to two oxygen atoms.
- the T unit is a unit composed of a trivalent group in which a silicon atom is bonded to three oxygen atoms.
- the Q unit is a unit composed of a tetravalent group in which a silicon atom is bonded to four oxygen atoms. Information on the content of these units can be obtained by Si-NMR.
- Examples of the airgel of this embodiment include those having the following structure. When an airgel has these structures, it becomes easy to express the outstanding heat conductivity and compression elastic modulus. In the present embodiment, the airgel may have any of the following structures.
- the airgel of this embodiment can have a structure represented by the following general formula (1).
- the airgel of this embodiment can have a structure represented by the following general formula (1a) as a structure including the structure represented by the formula (1).
- the structures represented by the formulas (1) and (1a) can be introduced into the skeleton of the airgel.
- R 1 and R 2 each independently represent an alkyl group or an aryl group
- R 3 and R 4 each independently represent an alkylene group.
- examples of the aryl group include a phenyl group and a substituted phenyl group.
- the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
- p represents an integer of 3 to 15.
- two or more R 1 s may be the same or different, and similarly, two or more R 2 s may be the same or different.
- two R 3 s may be the same or different, and similarly, two R 4 s may be the same or different.
- the airgel has a low thermal conductivity and is flexible.
- R 1 and R 2 each independently include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like. And a methyl group.
- R 3 and R 4 each independently include an alkylene group having 1 to 6 carbon atoms, and examples of the alkylene group include an ethylene group and a propylene group. Is mentioned.
- p can be 3 to 15, and may be 6 to 12.
- the airgel of the present embodiment may be an airgel having a ladder type structure including a column part and a bridge part, and the airgel represented by the following general formula (2).
- a ladder structure having a bridge portion represented by the general formula (2) can be introduced into the skeleton of the airgel.
- the “ladder structure” has two struts and bridges connecting the struts (having a so-called “ladder” form). It is.
- the airgel skeleton may have a ladder structure, but the airgel may partially have a ladder structure.
- R 5 and R 6 each independently represents an alkyl group or an aryl group, and b represents an integer of 3 to 15.
- examples of the aryl group include a phenyl group and a substituted phenyl group.
- examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
- two or more R 5 s may be the same or different, and similarly two or more R 6 s may be the same or different.
- the airgel has a structure derived from a conventional ladder-type silsesquioxane (that is, has a structure represented by the following general formula (X)). It becomes the airgel which has the outstanding softness
- Silsesquioxane is a polysiloxane having a composition formula: (RSiO 1.5 ) n and can have various skeleton structures such as a cage type, a ladder type, and a random type.
- the structure of the bridging portion is —O— (having the T unit as a structural unit).
- the structure of the bridge portion is a structure (polysiloxane structure) represented by the general formula (2).
- the airgel of the present embodiment may further have a structure derived from silsesquioxane in addition to the structures represented by the general formulas (1) to (3).
- R represents a hydroxy group, an alkyl group or an aryl group.
- the ladder structure has the following general formula ( The ladder type structure represented by 3) is mentioned.
- R 5 , R 6 , R 7 and R 8 each independently represents an alkyl group or an aryl group
- a and c each independently represent an integer of 1 to 3000
- b is 3 to 15
- examples of the aryl group include a phenyl group and a substituted phenyl group.
- examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group.
- two or more R 5 s may be the same or different, and similarly two or more R 6 s may be the same or different.
- when a is an integer of 2 or more two or more R 7 s may be the same or different.
- c is an integer of 2 or more
- 2 or more R 8 may be the same or different.
- R 5 , R 6 , R 7 and R 8 (however, R 7 and R 8 are only in formula (3)) Each independently includes an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like, and examples of the alkyl group include a methyl group.
- a and c can be independently 6 to 2000, but may be 10 to 1000.
- b can be 3 to 15, but may be 6 to 12.
- the manufacturing method of an airgel is demonstrated.
- the manufacturing method of an airgel is not specifically limited, For example, it can manufacture with the following method.
- the airgel of this embodiment includes a sol generation step, a wet gel generation step in which the sol obtained in the sol generation step is gelled and then aged to obtain a wet gel, and the wet gel obtained in the wet gel generation step.
- the “sol” is a state before the gelation reaction occurs, and in the present embodiment, the polysiloxane compound group and, in some cases, the silicon compound group are dissolved or dispersed in a solvent.
- the wet gel means a gel solid in a wet state that contains a liquid medium but does not have fluidity.
- generation process is a process which mixes the above-mentioned polysiloxane compound and a silicon compound and a solvent as needed, and hydrolyzes it, and produces
- an acid catalyst can be further added to the solvent to promote the hydrolysis reaction.
- a surfactant, a thermohydrolyzable compound, or the like can be added to the solvent.
- alcohols for example, water or a mixed solution of water and alcohols can be used.
- alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, and t-butanol.
- alcohols having a low surface tension and a low boiling point that can easily reduce the interfacial tension with the gel wall include methanol, ethanol, 2-propanol, and the like. These may be used alone or in admixture of two or more.
- the amount of alcohols when used as the solvent, can be 4 to 8 moles with respect to 1 mole of the total amount of the polysiloxane compound group and the silicon compound group, but can also be 4 to 6.5 moles. It may be 4.5 to 6 mol.
- the amount of alcohols 4 mol or more it becomes easier to obtain good compatibility, and by making the amount 8 mol or less, it becomes easier to suppress gel shrinkage.
- the acid catalyst examples include hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, bromic acid, chloric acid, chlorous acid, hypochlorous acid, and other inorganic acids; acidic phosphoric acid Acidic phosphates such as aluminum, acidic magnesium phosphate and acidic zinc phosphate; organic 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 Etc. Among these, organic carboxylic acids are mentioned as an acid catalyst which improves the water resistance of the obtained airgel more. Examples of the organic carboxylic acids include acetic acid, but may be formic acid, propionic acid, oxalic acid, malonic acid and the like. These may be used alone or in admixture of two or more.
- the addition amount of the acid catalyst can be 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of the polysiloxane compound group and the silicon compound group.
- a nonionic surfactant As the surfactant, a nonionic surfactant, an ionic surfactant, or the like can be used. These may be used alone or in admixture of two or more.
- nonionic surfactant for example, a compound containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group, a compound containing a hydrophilic part such as polyoxypropylene, and the like can be used.
- the compound containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether and the like.
- the compound having a hydrophilic portion such as polyoxypropylene include polyoxypropylene alkyl ether, a block copolymer of polyoxyethylene and polyoxypropylene, and the like.
- Examples of the ionic surfactant include a cationic surfactant, an anionic surfactant, and an amphoteric surfactant.
- Examples of the cationic surfactant include cetyltrimethylammonium bromide and cetyltrimethylammonium chloride, and examples of the anionic surfactant include sodium dodecylsulfonate.
- Examples of amphoteric surfactants include amino acid surfactants, betaine surfactants, amine oxide surfactants, and the like.
- Examples of amino acid surfactants include acyl glutamic acid.
- Examples of betaine surfactants include lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, and the like.
- Examples of amine oxide surfactants include lauryl dimethylamine oxide.
- surfactants have the effect of reducing the difference in chemical affinity between the solvent in the reaction system and the growing siloxane polymer and suppressing phase separation in the wet gel formation process described later. To do.
- the amount of the surfactant added depends on the type of the surfactant, or the types and amounts of the polysiloxane compound and the silicon compound.
- the amount of the surfactant added is 100 parts by mass with respect to 100 parts by mass of the total amount of the polysiloxane compound group and the silicon compound group. Although it can be ⁇ 100 parts by mass, it may be further 5 ⁇ 60 parts by mass.
- thermohydrolyzable compound generates a base catalyst by thermal hydrolysis, renders the reaction solution basic, and promotes a sol-gel reaction in a wet gel generation process described later. Accordingly, the thermohydrolyzable compound is not particularly limited as long as it can make the reaction solution basic after hydrolysis.
- Urea formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N -Acid amides such as methylacetamide and N, N-dimethylacetamide; cyclic nitrogen compounds such as hexamethylenetetramine and the like.
- urea is particularly easy to obtain the above-mentioned promoting effect.
- the addition amount of the thermohydrolyzable compound is not particularly limited as long as it can sufficiently promote the sol-gel reaction in the wet gel generation step described later.
- the amount added can be 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of the polysiloxane compound group and the silicon compound group. It may be up to 150 parts by mass.
- the hydrolysis in the sol production step depends on the types and amounts of the polysiloxane compound, silicon compound, acid catalyst, surfactant, etc. in the mixed solution, but for example, under a temperature environment of 20 to 60 ° C. for 10 minutes. It may be carried out for up to 24 hours, or in a temperature environment of 50 to 60 ° C. for 5 minutes to 8 hours.
- the hydrolyzable functional group in a polysiloxane compound and a silicon compound is fully hydrolyzed, and the hydrolysis product of a polysiloxane compound and the hydrolysis product of a silicon compound can be obtained more reliably.
- the temperature environment of the sol generation step may be adjusted to a temperature that suppresses hydrolysis of the thermohydrolyzable compound and suppresses gelation of the sol. .
- the temperature at this time may be any temperature as long as the hydrolysis of the thermally hydrolyzable compound can be suppressed.
- the temperature environment in the sol production step can be 0 to 40 ° C., but may be 10 to 30 ° C.
- the wet gel generation step is a step in which the sol obtained in the sol generation step is gelled and then aged to obtain a wet gel.
- a base catalyst can be used to promote gelation.
- Base catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; ammonium compounds such as ammonium hydroxide, ammonium fluoride, ammonium chloride, and ammonium bromide; sodium metaphosphate Basic sodium phosphates such as sodium pyrophosphate and 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 Aliphatic amines such as butylamine, propylamine, 3- (
- ammonium hydroxide (ammonia water) is excellent in that it has high volatility and does not easily remain in the airgel after drying, so that it is difficult to impair water resistance, and further, it is economical.
- the above base catalysts may be used alone or in admixture of two or more.
- the dehydration condensation reaction and / or dealcoholization condensation reaction of the polysiloxane compound group and the silicon compound group in the sol can be promoted, and the sol can be gelled in a shorter time. . Thereby, a wet gel with higher strength (rigidity) can be obtained.
- ammonia has high volatility and hardly remains in the airgel. Therefore, by using ammonia as a base catalyst, an airgel having better water resistance can be obtained.
- the addition amount of the base catalyst may be 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polysiloxane compound group and the silicon compound group, but may also be 1 to 4 parts by mass. By setting the addition amount to 0.5 parts by mass or more, gelation can be performed in a shorter time, and by setting the addition amount to 5 parts by mass or less, a decrease in water resistance can be further suppressed.
- the gelation of the sol in the wet gel generation step may be performed in a sealed container so that the solvent and the base catalyst do not volatilize.
- the gelation temperature can be 30 to 90 ° C., but it may be 40 to 80 ° C. By setting the gelation temperature to 30 ° C. or higher, gelation can be performed in a shorter time, and a wet gel with higher strength (rigidity) can be obtained. Moreover, since it becomes easy to suppress volatilization of a solvent (especially alcohol) by making gelation temperature into 90 degrees C or less, it can gelatinize, suppressing volume shrinkage.
- the aging in the wet gel generation step may be performed in a sealed container so that the solvent and the base catalyst do not volatilize.
- the aging temperature can be 30 to 90 ° C, but it may be 40 to 80 ° C.
- the aging temperature can be 30 to 90 ° C, but it may be 40 to 80 ° C.
- gelation of the sol and subsequent aging may be performed in a series of operations.
- the gelation time and aging time vary depending on the gelation temperature and aging temperature, but the total gelation time and aging time can be 4 to 480 hours, and may be 6 to 120 hours. By setting the total gelation time and aging time to 4 hours or more, a wet gel with higher strength (rigidity) can be obtained, and by setting it to 480 hours or less, the effect of aging can be more easily maintained.
- the gelation temperature and the aging temperature are increased within the above range, or the total time of the gelation time and the aging time is increased within the above range. be able to. Further, in order to increase the density of the obtained airgel or reduce the average pore diameter, the gelation temperature and the aging temperature are reduced within the above range, or the total time of the gelation time and the aging time is shortened within the above range. You can do it.
- the washing and solvent replacement step is a step of washing the wet gel obtained by the wet gel generation step (washing step), and a step of replacing the washing liquid in the wet gel with a solvent suitable for the drying conditions (the drying step described later). It is a process which has (solvent substitution process).
- the washing and solvent replacement step can be performed in a form in which only the solvent replacement step is performed without performing the step of washing the wet gel, but the impurities such as unreacted substances and by-products in the wet gel are reduced, and more The wet gel may be washed from the viewpoint of enabling the production of a highly pure airgel.
- the wet gel obtained in the wet gel production step is washed.
- the washing can be repeatedly performed using, for example, water or an organic solvent. At this time, washing efficiency can be improved by heating.
- Organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, acetonitrile, hexane, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran, methylene chloride , N, N-dimethylformamide, dimethyl sulfoxide, acetic acid, formic acid, and other various organic solvents can be used. You may use said organic solvent individually or in mixture of 2 or more types.
- a low surface tension solvent can be used in order to suppress gel shrinkage due to drying.
- low surface tension solvents generally have very low mutual solubility with water. Therefore, when using a low surface tension solvent in the solvent replacement step, examples of the organic solvent used in the washing step include hydrophilic organic solvents having high mutual solubility in both water and a low surface tension solvent. Note that the hydrophilic organic solvent used in the washing step can serve as a preliminary replacement for the solvent replacement step.
- examples of hydrophilic organic solvents include methanol, ethanol, 2-propanol, acetone, and methyl ethyl ketone. Methanol, ethanol, methyl ethyl ketone and the like are excellent in terms of economy.
- the amount of water or organic solvent used in the washing step can be an amount that can be sufficiently washed by replacing the solvent in the wet gel.
- the amount can be 3 to 10 times the volume of the wet gel.
- the washing can be repeated until the moisture content in the wet gel after washing is 10% by mass or less with respect to the silica mass.
- the temperature environment in the washing step can be a temperature not higher than the boiling point of the solvent used for washing.
- the temperature can be raised to about 30 to 60 ° C.
- the solvent of the washed wet gel is replaced with a predetermined replacement solvent in order to suppress shrinkage in the drying step described later.
- the replacement efficiency can be improved by heating.
- Specific examples of the solvent for substitution include a low surface tension solvent described later in the drying step when drying under atmospheric pressure at a temperature lower than the critical point of the solvent used for drying.
- examples of the substitution solvent include ethanol, methanol, 2-propanol, dichlorodifluoromethane, carbon dioxide, and the like, or a mixture of two or more thereof.
- Examples of the low surface tension solvent include a solvent having a surface tension at 20 ° C. of 30 mN / m or less. The surface tension may be 25 mN / m or less, or 20 mN / m or less.
- Examples of the low surface tension solvent include pentane (15.5), hexane (18.4), heptane (20.2), octane (21.7), 2-methylpentane (17.4), 3- Aliphatic hydrocarbons such as methylpentane (18.1), 2-methylhexane (19.3), cyclopentane (22.6), cyclohexane (25.2), 1-pentene (16.0); Aromatic hydrocarbons such as (28.9), toluene (28.5), m-xylene (28.7), p-xylene (28.3); dichloromethane (27.9), chloroform (27.2) ), Carbon tetrachloride (26.9), 1-chloropropane (21.8),
- aliphatic hydrocarbons hexane, heptane, etc.
- a hydrophilic organic solvent such as acetone, methyl ethyl ketone, 1,2-dimethoxyethane
- it can be used as the organic solvent in the washing step.
- a solvent having a boiling point of 100 ° C. or less at normal pressure may be used because it is easy to dry in the drying step described later. You may use said organic solvent individually or in mixture of 2 or more types.
- the amount of the solvent used in the solvent replacement step can be an amount that can sufficiently replace the solvent in the wet gel after washing.
- the amount can be 3 to 10 times the volume of the wet gel.
- the temperature environment in the solvent replacement step can be a temperature not higher than the boiling point of the solvent used for the replacement.
- the temperature can be increased to about 30 to 60 ° C.
- the drying method is not particularly limited, and known atmospheric pressure drying, supercritical drying, or freeze drying can be used. Among these, atmospheric drying or supercritical drying can be used from the viewpoint of easy production of low density airgel. Further, atmospheric drying can be used from the viewpoint of being able to produce at low cost.
- the normal pressure means 0.1 MPa (atmospheric pressure).
- the airgel of this embodiment can be obtained by drying a wet gel that has been washed and solvent-substituted at a temperature below the critical point of the solvent used for drying under atmospheric pressure.
- the drying temperature varies depending on the type of the solvent substituted, it is preferably set to 20 to 80 ° C. in view of the fact that drying at a high temperature increases the evaporation rate of the solvent and may cause a large crack in the gel. it can.
- the drying temperature may be further set to 30 to 60 ° C.
- the drying time varies depending on the wet gel volume and the drying temperature, but can be 4 to 120 hours.
- atmospheric pressure drying includes applying pressure within a range that does not inhibit productivity.
- the airgel of this embodiment can also be obtained by supercritical drying of a wet gel that has been washed and solvent-substituted.
- Supercritical drying can be performed by a known method. Examples of the supercritical drying method include a method of removing the solvent at a temperature and pressure higher than the critical point of the solvent contained in the wet gel.
- all or part of the solvent contained in the wet gel is obtained by immersing the wet gel in liquefied carbon dioxide, for example, at about 20 to 25 ° C. and about 5 to 20 MPa. And carbon dioxide having a lower critical point than that of the solvent, and then removing carbon dioxide alone or a mixture of carbon dioxide and the solvent.
- the airgel obtained by such normal pressure drying or supercritical drying may be further dried at 105 to 200 ° C. for about 0.5 to 2 hours under normal pressure. This makes it easier to obtain an airgel having a low density and small pores.
- the additional drying can be performed at 150 to 200 ° C. under normal pressure.
- the airgel of this embodiment obtained through the above steps has excellent heat insulating properties and productivity that have been difficult to achieve with conventional aerogels. Because of such advantages, the present invention can be applied to a use as a heat insulating material in the construction field, the automobile field, the home appliance, the semiconductor field, industrial equipment, and the like. Moreover, the airgel of this embodiment can be utilized as a coating additive, a cosmetic, an antiblocking agent, a catalyst carrier, etc. besides the use as a heat insulating material.
- Example 1 40.0 parts by mass of carbinol-modified siloxane “X-22-160AS” (manufactured by Shin-Etsu Chemical Co., Ltd., product name, average molecular weight 932 g / mol) represented by the above general formula (A) as a polysiloxane compound, silicon As a compound, methyltrimethoxysilane “LS-530” (manufactured by Shin-Etsu Chemical Co., Ltd., product name: hereinafter abbreviated as “MTMS”) is 60.0 parts by mass, water is 120.0 parts by mass, and methanol is 80.0 parts by mass.
- MTMS methyltrimethoxysilane
- a sol was obtained by adding 0.10 parts by mass of acetic acid as an acid catalyst and reacting at 25 ° C. for 8 hours.
- 40.0 parts by mass of 5% aqueous ammonia as a base catalyst was added, gelled at 60 ° C. for 8 hours, and then aged at 80 ° C. for 48 hours to obtain a wet gel.
- the obtained wet gel was immersed in 2500.0 parts by mass of methanol and washed at 60 ° C. for 12 hours. This washing operation was performed 3 times while exchanging with fresh methanol.
- the washed wet gel was immersed in 2500.0 parts by mass of heptane, which is a low surface tension solvent, and solvent substitution was performed at 60 ° C.
- Example 2 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, and 20.0 of cetyltrimethylammonium bromide (manufactured by Wako Pure Chemical Industries, Ltd .: hereinafter abbreviated as “CTAB”) as a cationic surfactant. 120.0 parts by mass of urea as a mass part and a thermohydrolyzable compound are mixed, and 40.0 parts by mass of X-22-160AS represented by the above general formula (A) as a polysiloxane compound and a silicon compound are mixed therewith. 60.0 parts by mass of MTMS was added and reacted at 25 ° C. for 2 hours to obtain a sol.
- CTAB cetyltrimethylammonium bromide
- the obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, an airgel 2 having a structure represented by the general formulas (1) and (1a) was obtained.
- Example 3 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed.
- the polysiloxane compound represented by the above general formula (B) is a bifunctional bifunctional alkoxy-modified polysiloxane compound (hereinafter referred to as “polysiloxane compound A” having an average molecular weight of 966 g / mol) of 40.0 parts by mass and silicon. 60.0 parts by mass of MTMS was added as a compound and reacted at 25 ° C. for 2 hours to obtain a sol.
- the obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, an airgel 3 having a ladder structure represented by the general formulas (2) and (3) was obtained.
- the “polysiloxane compound A” was synthesized as follows. First, in a 1 liter three-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser, 100.0 parts by mass of hydroxy-terminated dimethylpolysiloxane “XC96-723” (product name, manufactured by Momentive), methyl 181.3 parts by mass of trimethoxysilane and 0.50 parts by mass of t-butylamine were mixed and reacted at 30 ° C. for 5 hours. Thereafter, this reaction solution was heated at 140 ° C. for 2 hours under reduced pressure of 1.3 kPa to remove volatile components, thereby obtaining a bifunctional alkoxy-modified polysiloxane compound (polysiloxane compound A) at both ends.
- Example 4 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed. 20.0 parts by mass of polysiloxane compound A represented by the above general formula (B) as a polysiloxane compound and 80.0 parts by mass of MTMS as a silicon compound were added and reacted at 25 ° C. for 2 hours to obtain a sol. . The obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, an airgel 4 having a ladder structure represented by the general formulas (2) and (3) was obtained.
- Example 5 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed. 40.0 parts by mass of a polysiloxane compound represented by the above general formula (B), trifunctional alkoxy-modified polysiloxane compound at both ends (hereinafter referred to as “polysiloxane compound B”, average molecular weight 702 g / mol) and silicon 60.0 parts by mass of MTMS was added as a compound and reacted at 25 ° C. for 2 hours to obtain a sol.
- a polysiloxane compound represented by the above general formula (B) trifunctional alkoxy-modified polysiloxane compound at both ends
- silicon 60.0 parts by mass of MTMS was added as a compound and reacted at 25 ° C. for 2 hours to obtain a sol.
- the obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, an airgel 5 having a ladder structure represented by the general formulas (2) and (3) was obtained.
- the “polysiloxane compound B” was synthesized as follows. First, in a 1 liter three-necked flask equipped with a stirrer, a thermometer, and a Dimroth condenser, 100.0 parts by mass of XC96-723, 202.6 parts by mass of tetramethoxysilane and 0. 50 parts by mass was mixed and reacted at 30 ° C. for 5 hours. Thereafter, this reaction solution was heated at 140 ° C. for 2 hours under a reduced pressure of 1.3 kPa to remove volatile components, thereby obtaining a trifunctional alkoxy-modified polysiloxane compound (polysiloxane compound B) at both ends.
- Example 6 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed. 20.0 parts by mass of polysiloxane compound B represented by the above general formula (B) as a polysiloxane compound and 80.0 parts by mass of MTMS as a silicon compound were added and reacted at 25 ° C. for 2 hours to obtain a sol. . The obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, in the same manner as in Example 1, an airgel 6 having a ladder structure represented by the general formulas (2) and (3) was obtained.
- Example 2 200.0 parts by mass of water, 0.10 parts by mass of acetic acid as an acid catalyst, 20.0 parts by mass of CTAB as a cationic surfactant, and 120.0 parts by mass of urea as a thermohydrolyzable compound were mixed. 70.0 parts by mass of MTMS as a silicon compound and 30.0 parts by mass of dimethyldimethoxysilane “LS-520” (manufactured by Shin-Etsu Chemical Co., Ltd., product name: hereinafter abbreviated as “DMDMS”) were added at 25 ° C. A sol was obtained by reacting for a time. The obtained sol was gelled at 60 ° C. for 8 hours and then aged at 80 ° C. for 48 hours to obtain a wet gel. Thereafter, airgel 8 was obtained in the same manner as in Example 1.
- Table 1 summarizes drying methods and Si raw materials (polysiloxane compounds and silicon compounds) in each Example and Comparative Example.
- the thermal conductivity was measured using a steady-state thermal conductivity measuring device “HFM436 Lambda” (manufactured by NETZSCH, product name).
- the measurement conditions were an average temperature of 25 ° C. under atmospheric pressure.
- the measurement sample obtained as described above is sandwiched between the upper and lower heaters with a load of 0.3 MPa, the temperature difference ⁇ T is set to 20 ° C., and the guard sample is adjusted so as to obtain a one-dimensional heat flow. Upper surface temperature, lower surface temperature, etc. were measured.
- thermal resistance RS of the measurement sample was calculated
- R S N ((T U ⁇ T L ) / Q) ⁇ R O
- T U represents a measurement sample top surface temperature
- T L represents the measurement sample lower surface temperature
- R O represents the thermal contact resistance of the upper and lower interfaces
- Q is shows the heat flux meter output.
- N is a proportionality coefficient, and is obtained in advance using a calibration sample.
- a small tabletop testing machine “EZTest” manufactured by Shimadzu Corporation, product name
- 500N was used as a load cell.
- an upper platen ( ⁇ 20 mm) and a lower platen ( ⁇ 118 mm) made of stainless steel were used as compression measurement jigs.
- a measurement sample was set between an upper platen and a lower platen arranged in parallel, and compression was performed at a speed of 1 mm / min.
- the measurement temperature was 25 ° C., and the measurement was terminated when a load exceeding 500 N was applied or when the measurement sample was destroyed.
- the strain ⁇ was obtained from the following equation.
- ⁇ ⁇ d / d1
- ⁇ d the displacement (mm) of the thickness of the measurement sample due to the load
- d1 the thickness (mm) of the measurement sample before the load is applied.
- the compressive stress ⁇ (MPa) was obtained from the following equation.
- ⁇ F / A
- F represents the compressive force (N)
- A represents the cross-sectional area (mm 2 ) of the measurement sample before applying a load.
- the compressive elastic modulus E (MPa) was obtained from the following equation in the compression force range of 0.1 to 0.2N.
- E ( ⁇ 2 ⁇ 1 ) / ( ⁇ 2 ⁇ 1 )
- ⁇ 1 indicates a compressive stress (MPa) measured at a compressive force of 0.1 N
- ⁇ 2 indicates a compressive stress (MPa) measured at a compressive force of 0.2 N
- ⁇ 1 indicates a compressive stress.
- the compressive strain measured at ⁇ 1 is shown
- ⁇ 2 shows the compressive strain measured at the compressive stress ⁇ 2 .
- d1 is the thickness of the measurement sample before the load is applied
- d2 is the thickness when the maximum load of 500 N is applied or the measurement sample is destroyed, and the load is removed.
- the thickness of the measurement sample was calculated as d3 according to the following equation.
- Deformation recovery rate (d3-d2) / (d1-d2) ⁇ 100
- Maximum compression deformation rate (d1 ⁇ d2) / d1 ⁇ 100
- the airgels of the examples all have a thermal conductivity of 0.03 W / m ⁇ K or less, a compression elastic modulus of 2 MPa or less, a deformation recovery rate of 90% or more, and a maximum compression deformation rate of 80% or more. It can be read that it has heat insulation and flexibility.
- Comparative Example 1 and Comparative Example 4 had a thermal conductivity of 0.03 W / m ⁇ K or less, but they were easily broken because of their large compressive modulus and brittleness against deformation. In Comparative Example 2, the thermal conductivity was large. Comparative Example 3 had sufficient flexibility but high thermal conductivity.
- the airgel of the present invention has excellent heat insulating properties and flexibility, which has been difficult to achieve with conventional airgels. Because of such advantages, the present invention can be applied to a use as a heat insulating material in the construction field, the automobile field, the home appliance, the semiconductor field, industrial equipment, and the like. Moreover, the airgel of this invention can be utilized as a coating additive, cosmetics, an antiblocking agent, a catalyst support body etc. other than the use as a heat insulating material.
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Abstract
Description
本明細書において、「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。本明細書に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。本明細書に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。「A又はB」とは、A及びBのどちらか一方を含んでいればよく、両方とも含んでいてもよい。本明細書に例示する材料は、特に断らない限り、1種を単独で又は2種以上を組み合わせて用いることができる。本明細書において、組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する複数の物質の合計量を意味する。
狭義には、湿潤ゲルに対して超臨界乾燥法を用いて得られた乾燥ゲルをエアロゲル、大気圧下での乾燥により得られた乾燥ゲルをキセロゲル、凍結乾燥により得られた乾燥ゲルをクライオゲルと称するが、本実施形態においては、湿潤ゲルのこれらの乾燥手法によらず、得られた低密度の乾燥ゲルを「エアロゲル」と称する。すなわち、本実施形態においてエアロゲルとは、広義のエアロゲルである「Gel comprised of a microporous solid in which the dispersed phase is a gas(分散相が気体である微多孔性固体から構成されるゲル)」を意味するものである。一般的にエアロゲルの内部は、網目状の微細構造となっており、2~20nm程度のエアロゲル粒子(エアロゲルを構成する粒子)が結合したクラスター構造を有している。このクラスターにより形成される骨格間には、100nmに満たない細孔がある。これにより、エアロゲルは、三次元的に微細な多孔性の構造を有している。なお、本実施形態におけるエアロゲルは、例えば、シリカを主成分とするシリカエアロゲルである。シリカエアロゲルとしては、例えば、有機基(メチル基等)又は有機鎖を導入した、いわゆる、有機-無機ハイブリッド化されたシリカエアロゲルが挙げられる。本実施形態のエアロゲルは、断熱性と生産性(柔軟性)とに優れたものである。
本実施形態のエアロゲルは、加水分解性の官能基又は縮合性の官能基を有しかつ平均分子量が300~1500g/molであるポリシロキサン化合物、及び、加水分解性の官能基を有するポリシロキサン化合物の加水分解生成物からなる群より選択される少なくとも一種を含有する上記のゾルの縮合物である湿潤ゲルの乾燥物である(上記のゾルから生成された湿潤ゲルを乾燥することで得られる)。なお、上記縮合物は、加水分解性の官能基を有するポリシロキサン化合物の加水分解により得られた加水分解生成物の縮合反応により得られてもよく、加水分解により得られた官能基ではない縮合性の官能基を有するポリシロキサン化合物の縮合反応により得られてもよい。ポリシロキサン化合物は、加水分解性の官能基及び縮合性の官能基の少なくとも一方を有していればよく、加水分解性の官能基及び縮合性の官能基の双方を有していてもよい。
次に、エアロゲルの製造方法について説明する。エアロゲルの製造方法は、特に限定されないが、例えば以下の方法により製造することができる。
ゾル生成工程は、上述のポリシロキサン化合物及び必要に応じケイ素化合物と溶媒とを混合し、加水分解させてゾルを生成する工程である。本工程においては、加水分解反応を促進させるため、溶媒中にさらに酸触媒を添加することができる。また、特許第5250900号公報に示されるように、溶媒中に界面活性剤、熱加水分解性化合物等を添加することもできる。
湿潤ゲル生成工程は、ゾル生成工程で得られたゾルをゲル化し、その後熟成して湿潤ゲルを得る工程である。本工程では、ゲル化を促進させるため塩基触媒を用いることができる。
洗浄及び溶媒置換工程は、上記湿潤ゲル生成工程により得られた湿潤ゲルを洗浄する工程(洗浄工程)と、湿潤ゲル中の洗浄液を乾燥条件(後述の乾燥工程)に適した溶媒に置換する工程(溶媒置換工程)を有する工程である。洗浄及び溶媒置換工程は、湿潤ゲルを洗浄する工程を行わず、溶媒置換工程のみを行う形態でも実施可能であるが、湿潤ゲル中の未反応物、副生成物等の不純物を低減し、より純度の高いエアロゲルの製造を可能にする観点からは、湿潤ゲルを洗浄してもよい。
乾燥工程では、上記のとおり洗浄及び溶媒置換した湿潤ゲルを乾燥させる。これにより、最終的にエアロゲルを得ることができる。すなわち、上記ゾルから生成された湿潤ゲルを乾燥してなるエアロゲルを得ることができる。
(実施例1)
ポリシロキサン化合物として上記一般式(A)で表されるカルビノール変性シロキサン「X-22-160AS」(信越化学工業株式会社製、製品名、平均分子量932g/mol)を40.0質量部、ケイ素化合物としてメチルトリメトキシシラン「LS-530」(信越化学工業株式会社製、製品名:以下『MTMS』と略記)を60.0質量部、水を120.0質量部及びメタノールを80.0質量部混合し、これに酸触媒として酢酸を0.10質量部加え、25℃で8時間反応させてゾルを得た。得られたゾルに、塩基触媒として5%濃度のアンモニア水を40.0質量部加え、60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後、得られた湿潤ゲルをメタノール2500.0質量部に浸漬し、60℃で12時間かけて洗浄を行った。この洗浄操作を、新しいメタノールに交換しながら3回行った。次に、洗浄した湿潤ゲルを、低表面張力溶媒であるヘプタン2500.0質量部に浸漬し、60℃で12時間かけて溶媒置換を行った。この溶媒置換操作を、新しいヘプタンに交換しながら3回行った。洗浄及び溶媒置換された湿潤ゲルを、常圧下にて、40℃で96時間乾燥し、その後さらに150℃で2時間乾燥することで、上記一般式(1)及び(1a)で表される構造を有するエアロゲル1を得た。
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤として臭化セチルトリメチルアンモニウム(和光純薬工業株式会社製:以下『CTAB』と略記)を20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにポリシロキサン化合物として上記一般式(A)で表されるX-22-160ASを40.0質量部及びケイ素化合物としてMTMSを60.0質量部加え、25℃で2時間反応させてゾルを得た。得られたゾルを60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後は、実施例1と同様にして、上記一般式(1)及び(1a)で表される構造を有するエアロゲル2を得た。
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにポリシロキサン化合物として上記一般式(B)で表される、両末端2官能アルコキシ変性ポリシロキサン化合物(以下、「ポリシロキサン化合物A」という、平均分子量966g/mol)を40.0質量部及びケイ素化合物としてMTMSを60.0質量部加え、25℃で2時間反応させてゾルを得た。得られたゾルを60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後は、実施例1と同様にして、上記一般式(2)及び(3)で表されるラダー型構造を有するエアロゲル3を得た。
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにポリシロキサン化合物として上記一般式(B)で表されるポリシロキサン化合物Aを20.0質量部及びケイ素化合物としてMTMSを80.0質量部加え、25℃で2時間反応させてゾルを得た。得られたゾルを60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後は、実施例1と同様にして、上記一般式(2)及び(3)で表されるラダー型構造を有するエアロゲル4を得た。
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにポリシロキサン化合物として上記一般式(B)で表される、両末端3官能アルコキシ変性ポリシロキサン化合物(以下、「ポリシロキサン化合物B」という、平均分子量702g/mol)を40.0質量部及びケイ素化合物としてMTMSを60.0質量部加え、25℃で2時間反応させてゾルを得た。得られたゾルを60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後は、実施例1と同様にして、上記一般式(2)及び(3)で表されるラダー型構造を有するエアロゲル5を得た。
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにポリシロキサン化合物として上記一般式(B)で表されるポリシロキサン化合物Bを20.0質量部及びケイ素化合物としてMTMSを80.0質量部加え、25℃で2時間反応させてゾルを得た。得られたゾルを60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後は、実施例1と同様にして、上記一般式(2)及び(3)で表されるラダー型構造を有するエアロゲル6を得た。
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにケイ素化合物としてMTMSを100.0質量部加え、25℃で2時間反応させてゾルを得た。得られたゾルを60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後は、実施例1と同様にして、エアロゲル7を得た。
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにケイ素化合物としてMTMSを70.0質量部及びジメチルジメトキシシラン「LS-520」(信越化学工業株式会社製、製品名:以下『DMDMS』と略記)を30.0質量部加え、25℃で2時間反応させてゾルを得た。得られたゾルを60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後は、実施例1と同様にして、エアロゲル8を得た。
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにケイ素化合物としてMTMSを60.0質量部及びDMDMSを40.0質量部加え、25℃で2時間反応させてゾルを得た。得られたゾルを60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後は、実施例1と同様にして、エアロゲル9を得た。
水を200.0質量部、酸触媒として酢酸を0.10質量部、カチオン系界面活性剤としてCTABを20.0質量部及び熱加水分解性化合物として尿素を120.0質量部混合し、これにケイ素化合物としてMTMSを100.0質量部加え、25℃で2時間反応させてゾルを得た。得られたゾルを60℃で8時間ゲル化した後、80℃で48時間熟成して湿潤ゲルを得た。その後、得られた湿潤ゲルをメタノール2500.0質量部に浸漬し、60℃で12時間かけて洗浄を行った。この洗浄操作を、新しいメタノールに交換しながら3回行った。次に、洗浄した湿潤ゲルを、2-プロパノール2500.0質量部に浸漬し、60℃で12時間かけて溶媒置換を行った。この溶媒置換操作を、新しい2-プロパノールに交換しながら3回行った。
各実施例及び比較例で得られたエアロゲル1~10について、以下の条件に従って熱伝導率、圧縮弾性率、最大圧縮変形率、変形回復率、密度及び気孔率を測定し、評価した。評価結果をまとめて表2に示す。
刃角約20~25度の刃を用いて、エアロゲルを150mm×150mm×100mmのサイズに加工し、測定サンプルとした。次に、面の平行を確保するために、必要に応じて#1500以上の紙やすりで整形した。得られた測定サンプルを、熱伝導率測定前に、定温乾燥機「DVS402」(ヤマト科学株式会社製、製品名)を用いて、大気圧下、100℃で30分間乾燥した。次いで測定サンプルをデシケータ中に移し、25℃まで冷却した。
RS=N((TU-TL)/Q)-RO
式中、TUは測定サンプル上面温度を示し、TLは測定サンプル下面温度を示し、ROは上下界面の接触熱抵抗を示し、Qは熱流束計出力を示す。なお、Nは比例係数であり、較正試料を用いて予め求めておいた。
λ=d/RS
式中、dは測定サンプルの厚さを示す。
刃角約20~25度の刃を用いて、エアロゲルを7.0mm角の立方体(サイコロ状)に加工し、測定サンプルとした。次に、面の平行を確保するために、必要に応じて#1500以上の紙やすりで測定サンプルを整形した。得られた測定サンプルを、熱伝導率測定前に、定温乾燥機「DVS402」(ヤマト科学株式会社製、製品名)を用いて、大気圧下、100℃で30分間乾燥した。次いで測定サンプルをデシケータ中に移し、25℃まで冷却した。
ε=Δd/d1
式中、Δdは負荷による測定サンプルの厚みの変位(mm)を示し、d1は負荷をかける前の測定サンプルの厚み(mm)を示す。
また、圧縮応力σ(MPa)は、次式より求めた。
σ=F/A
式中、Fは圧縮力(N)を示し、Aは負荷をかける前の測定サンプルの断面積(mm2)を示す。
E=(σ2-σ1)/(ε2-ε1)
式中、σ1は圧縮力が0.1Nにおいて測定される圧縮応力(MPa)を示し、σ2は圧縮力が0.2Nにおいて測定される圧縮応力(MPa)を示し、ε1は圧縮応力σ1において測定される圧縮ひずみを示し、ε2は圧縮応力σ2において測定される圧縮ひずみを示す。
変形回復率=(d3-d2)/(d1-d2)×100
最大圧縮変形率=(d1-d2)/d1×100
エアロゲルについての、3次元網目状に連続した通孔(細孔)の中心細孔径、密度及び気孔率は、DIN66133に準じて水銀圧入法により測定した。なお、測定温度を室温(25℃)とし、測定装置としては、オートポアIV9520(株式会社島津製作所製、製品名)を用いた。
Claims (13)
- 加水分解性の官能基又は縮合性の官能基を有しかつ平均分子量が300~1500g/molであるポリシロキサン化合物、及び、該加水分解性の官能基を有するポリシロキサン化合物の加水分解生成物からなる群より選択される少なくとも一種を含有するゾルの縮合物である湿潤ゲルの乾燥物であるエアロゲル。
- 前記縮合性の官能基がヒドロキシアルキル基である、請求項1~3のいずれか一項記載のエアロゲル。
- 前記ヒドロキシアルキル基の炭素数が1~6である、請求項6記載のエアロゲル。
- 前記加水分解性の官能基がアルコキシ基である、請求項1、4及び5のいずれか一項記載のエアロゲル。
- 前記アルコキシ基の炭素数が1~6である、請求項9記載のエアロゲル。
- 前記ゾルが、加水分解性の官能基又は縮合性の官能基を有するケイ素化合物、及び、該加水分解性の官能基を有するケイ素化合物の加水分解生成物からなる群より選択される少なくとも一種をさらに含有する、請求項1~11のいずれか一項記載のエアロゲル。
- 前記乾燥物が、前記湿潤ゲルの乾燥に用いられる溶媒の臨界点未満の温度及び大気圧下で行われる乾燥により得られる、請求項1~12のいずれか一項記載のエアロゲル。
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US10391466B2 (en) * | 2017-06-02 | 2019-08-27 | Lawrence Livermore National Security, Llc | Fabrication of nanoporous aerogels via freeze substitution of nanowire suspensions |
CN111072037B (zh) * | 2020-02-10 | 2023-04-28 | 赢胜节能集团股份有限公司 | 一种二氧化硅气凝胶的制备方法 |
CN111232989B (zh) * | 2020-02-10 | 2023-01-20 | 佛山市农芯智能科技有限公司 | 一种含多烷氧基硅基苯化合物及杂化二氧化硅气凝胶 |
CN112744820A (zh) * | 2021-01-21 | 2021-05-04 | 江苏泛亚微透科技股份有限公司 | 一种甲基硅倍半氧烷气凝胶的绿色制备方法 |
CN112875711B (zh) * | 2021-01-26 | 2022-06-21 | 西南科技大学 | 一种梯度密度疏水氧化硅气凝胶的制备方法 |
CN113980342B (zh) * | 2021-08-19 | 2022-12-30 | 中国科学技术大学 | 一种有机硅聚合物形状记忆气凝胶及其制备方法 |
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JP2018076231A (ja) | 2018-05-17 |
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KR20180044260A (ko) | 2018-05-02 |
JPWO2017038775A1 (ja) | 2018-03-22 |
CN107922202A (zh) | 2018-04-17 |
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US10227455B2 (en) | 2019-03-12 |
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