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WO2018030796A1 - Précurseur d'aérogel, son procédé de préparation, aérogel préparé à partir de celui-ci, et procédé de préparation d'aérogel l'utilisant - Google Patents

Précurseur d'aérogel, son procédé de préparation, aérogel préparé à partir de celui-ci, et procédé de préparation d'aérogel l'utilisant Download PDF

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Publication number
WO2018030796A1
WO2018030796A1 PCT/KR2017/008650 KR2017008650W WO2018030796A1 WO 2018030796 A1 WO2018030796 A1 WO 2018030796A1 KR 2017008650 W KR2017008650 W KR 2017008650W WO 2018030796 A1 WO2018030796 A1 WO 2018030796A1
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group
unsubstituted
substituted
formula
airgel
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PCT/KR2017/008650
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English (en)
Korean (ko)
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오경실
최희정
장영래
이제균
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주식회사 엘지화학
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Priority to JP2019501896A priority Critical patent/JP6672524B2/ja
Priority to US15/772,681 priority patent/US10773964B2/en
Priority to EP17839814.5A priority patent/EP3357927B1/fr
Priority to CN201780004155.4A priority patent/CN108368135B/zh
Priority claimed from KR1020170101114A external-priority patent/KR101896846B1/ko
Publication of WO2018030796A1 publication Critical patent/WO2018030796A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages

Definitions

  • the present invention relates to an airgel precursor, a method for preparing the same, an airgel prepared therefrom, and a method for preparing an airgel using the same. It relates to a manufacturing method.
  • Aerogels are porous materials with 98% of the total volume of air in which SiO 2 nanostructures are coarsely woven like a nonwoven fabric. Aerogels have high porosity, nano-level micropores, and high specific surface area, resulting in ultra-light weight, high thermal insulation, and low dielectric properties. As a result, researches are being actively conducted as insulation materials and environmentally friendly high-temperature insulation materials, ultra-low dielectric thin films for highly integrated devices, catalysts and catalyst carriers, electrodes for supercapacitors or seawater desalination.
  • airgel is super-insulation, which shows a thermal conductivity of 0.300 W / m ⁇ K or lower, which is lower than that of conventional thermal insulation such as styrofoam.
  • airgel has been used as a high temperature insulation material because there is no fear of fire vulnerabilities and the generation of harmful gases in case of fire, which is a fatal weakness of the organic insulation material.
  • surface hydrophobization treatment is essential to prevent moisture penetration.
  • the hydrophobic group on the surface of the airgel is not oxidized by heat, it may exhibit excellent durability.
  • TEOS tetraethoxysilane
  • hydrolyzed TEOS is used as a precursor when synthesizing aerogels, and water, alcohol, and acid or base catalysts are used to control the porosity of the wet gel, and after hydrophobic surface modification, Aerogels having hydrophobicity were prepared through supercritical drying and atmospheric pressure drying.
  • the reaction efficiency is lower than that of the liquid phase which is a single phase because it is a liquid / solid two phase. Therefore, a large amount of surface hydrophobization agent is used in the surface hydrophobization treatment of the wet gel, and as a result, the surface hydrophobization agent is easily oxidized by heat, thereby deteriorating high temperature durability.
  • Another object of the present invention is to provide an airgel excellent in both room temperature and high temperature hydrophobicity, high temperature stability and heat insulation.
  • Still another object of the present invention is to provide an airgel blanket having excellent room temperature and high temperature hydrophobicity, high temperature stability, and thermal insulation.
  • Still another object of the present invention is to provide a method for preparing an airgel that does not undergo a separate solvent replacement process.
  • the present invention comprises at least one selected from the group consisting of structural units represented by the following formula (1) and structural units represented by the following formulas (2) to (4) in a molar ratio of 100: 1 to 100: 20, and the weight average molecular weight
  • An airgel precursor is characterized in that it is 1,000 to 6,000 g / mol and has a viscosity of 2.0 to 4.0 cps after heating at 45 to 60 ° C. for 24 hours:
  • L 1 to L 4 are the same as or different from each other, and each independently, a direct bond or O,
  • X is Si, Ti, Zr, Hf or Rf,
  • R 1 is a substituted or unsubstituted C 1 to C 20 linear alkyl group, a substituted or unsubstituted C 3 to C 20 branched or cyclic alkyl group, a substituted or unsubstituted C 2 to C 20 linear alkenyl group, Substituted or unsubstituted C 4 to C 20 linear alkenyl group, substituted or unsubstituted C 2 to C 20 linear alkynyl group, or substituted or unsubstituted C 5 to C 20 aryl group,
  • R 2 is a halogen, hydroxyl group, substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted C 1 to C 20 alkyloyl group, substituted or unsubstituted C 1 to C 20 alkyloocta It's time.
  • the present invention is a first step of preparing a mixture by mixing a compound represented by the formula (21) and a compound represented by the formula (22) with an alcohol in a molar ratio of 100: 1 to 100: 20; And a second step of hydrolyzing and polycondensing the mixture.
  • R is a substituted or unsubstituted C 1 to C 20 linear alkyl group or a substituted or unsubstituted C 3 to C 20 branched or cyclic alkyl group,
  • X is Si, Ti, Zr, Hf or Rf,
  • R 1 is a substituted or unsubstituted C 1 to C 20 linear alkyl group, a substituted or unsubstituted C 3 to C 20 branched or cyclic alkyl group, a substituted or unsubstituted C 2 to C 20 linear alkenyl group, A substituted or unsubstituted C 4 to C 20 branched alkenyl group, a substituted or unsubstituted C 2 to C 20 linear alkynyl group, or a substituted or unsubstituted C 5 to C 20 aryl group,
  • R 2 is a halogen, hydroxyl group, substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted C 1 to C 20 alkyloyl group, substituted or unsubstituted C 1 to C 20 alkyloocta It's time.
  • the present invention comprises the steps of mixing the airgel precursor and the base catalyst to form a wet gel at pH ⁇ 3; Surface modification by mixing the wet gel and a hydrophobic agent; And it provides a method for producing an airgel comprising the step of drying the surface modification gel.
  • the airgel precursor according to the present invention has excellent room temperature and high temperature hydrophobicity, excellent durability, and can be used while mass storage for a long time.
  • the airgel precursor of the present invention is imparted hydrophobicity to the wet gel produced during the preparation of the airgel, so that compatibility of the wet gel and the organic solvent can be improved, thereby increasing the efficiency during surface modification, surface modification You can also reduce the amount of material you use.
  • the airgel and the airgel blanket of the present invention may be excellent in both room temperature and high temperature hydrophobicity, high temperature stability and thermal insulation.
  • Figure 2 is a graph showing the distribution of pores in the airgel of Example 5 and Comparative Example 3.
  • 'substituted or unsubstituted' is deuterium; Cyano group; C 1 to C 20 linear alkyl group; C 3 to C 20 branched alkyl group; C 2 Through C 20 Linear alkenyl group; Branched alkenyl groups of C 4 to C 20 ; C 2 to C 20 linear alkynyl group; It means unsubstituted or substituted with one or more substituents selected from the group consisting of a C 3 to C 20 cycloalkyl group and a C 6 to C 20 aryl group.
  • site means a site linked with other substituents or structural units.
  • Airgel precursor according to an embodiment of the present invention is a structural unit represented by the following formula (1) and at least one selected from the group consisting of structural units represented by the formula 2 to 4 in a molar ratio of 100: 1 to 100: 20
  • the weight average molecular weight is 1,000 to 6,000 g / mol, and the viscosity is 2.0 to 4.0 cps after heating at 45 to 60 ° C for 24 hours.
  • L 1 to L 4 are the same as or different from each other, and each independently, a direct bond or O,
  • X may be Si, Ti, Zr, Hf or Rf, more specifically Si.
  • R 1 is a hydrophobic functional group which imparts hydrophobicity to the airgel precursor.
  • the alkyl group may be a substituted or unsubstituted C 1 to C 10 linear alkyl group or a substituted or unsubstituted C 3 to C 10 branched alkyl group, specific examples thereof include methyl group, ethyl group, propyl group, butyl group, Pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, isobutyl, sec-butyl and tert-butyl, isopentyl, neopentyl, isohexyl, isoheptyl, isooctyl, isononyl, Or isodecyl.
  • the cyclic alkyl group includes C 3 to C 20 monocyclic or polycyclic, and the polycyclic may mean a group directly connected or condensed with another ring group.
  • the other ring group here may be a cyclo alkyl group, hetero cyclo alkyl group, aryl group or heteroaryl group.
  • the cycloalkyl group may be a substituted or unsubstituted C 3 to C 10 cycloalkyl group, specific examples thereof include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, Cyclononyl group, a cyclodecyl group, etc. are mentioned.
  • the alkenyl group may be a substituted or unsubstituted C 2 to C 10 linear alkenyl group, a substituted or unsubstituted C 4 to C 10 branched alkenyl group, specific examples thereof may be an ethenyl group, propenyl group, butene And a vinyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, or decenyl group.
  • the alkynyl group may be a substituted or unsubstituted C 2 to C 10 linear alkynyl group, and specific examples thereof include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, and noninyl group. Or a decinyl group.
  • the aryl group includes monocyclic or polycyclic, and the polycyclic means a group in which aryl is directly connected or condensed with another ring group.
  • Specific examples of the aryl group include phenyl group, biphenyl group, triphenyl, naphthyl group, anthryl group, phenanthrenyl group, pyrenyl group or fluorenyl group.
  • R 1 may be a substituted or unsubstituted C 1 to C 20 linear alkyl group or a substituted or unsubstituted C 3 to C 20 branched group, and more specifically, may be a methyl group.
  • R 2 are each independently the same as or different from each other and are a halogen, a hydroxyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 1 to C 20 alkyloyl group, a substituted or unsubstituted It may be a C 1 to C 20 alkylooxy group, specifically, it may be a halogen, a hydroxyl group or an unsubstituted C 1 to C 20 alkoxy group.
  • the halogen may be one selected from the group consisting of F, Cl, Br, I, and At, and specifically, the halogen may be one selected from the group consisting of F, Cl, Br, and I.
  • the alkoxy group may be a C 1 to C 10 alkoxy group, and specific examples thereof include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group, octoxy group, nonoxy group or dodecyloxy, and the like. Can be.
  • alkylooxy group examples include an acetyl group, propionyl group, n-butyryloxy group or stearooxy group.
  • alkyloyloxy group examples include propionyloxy group, n-butyryloxy group, stearoyloxy group, and the like.
  • R 2 may be specifically an unsubstituted C 1 to C 20 alkoxy group, and more specifically, may be a methoxy group.
  • the airgel precursor is preferably at least one selected from the group consisting of a structural unit represented by the formula (1) and a structural unit represented by the following formulas 2 to 4 100: 1 to 100: 15, more preferably 100: It may be included in a molar ratio of 4 to 100: 10, the weight average molecular weight is preferably 1,000 to 5,500g / mol, more preferably 1,000 to 3,500g / mol.
  • the airgel precursor may have excellent hydrophobicity by itself. In addition, it is excellent in durability and can be mass-produced, and can be used in an airgel manufacturing process while storing for a long time after mass production.
  • the airgel precursor may impart hydrophobicity to the wet gel produced during the preparation of the airgel or the airgel blanket.
  • the wet gel imparted with hydrophobicity may improve compatibility with an organic solvent, thereby increasing efficiency in the surface modification process during the aerogel or airgel blanket manufacturing process, and reducing the amount of surface modifier used.
  • the airgel or airgel blanket prepared from the airgel precursor of the present invention is not only excellent in room temperature and high temperature hydrophobicity, but also in high temperature thermal stability and heat insulation.
  • the airgel precursor has a viscosity of 2.0 to 4.0 cps after heating at 45 to 60 ° C. for 24 hours, preferably 2.5 to 3.5 cps, more preferably 2.8 to 2.9 cps.
  • the airgel precursor may maintain the above-described viscosity range not only after heating but also before and during heating.
  • leaving the airgel precursor at 45 to 60 ° C. for 1 hour means to leave it at room temperature (23 ⁇ 3 ° C.) for 1 hour.
  • the airgel precursor satisfies all of the above-mentioned viscosity conditions at a temperature of 6 months or more at a viscosity of 2.0 to 4.0 cps, preferably 2.5 to 3.5 cps, more preferably 2.8 to 2.9 cps, and excellent durability. it means.
  • Si of the structural unit represented by Chemical Formula 1 in the airgel precursor may be connected to Si of the structural unit represented by Chemical Formula 1 via O (oxygen).
  • the airgel precursor may include a structural unit represented by Formula 5 below.
  • the airgel precursor may include one or more selected from the group consisting of structural units represented by the following Chemical Formulas 6 to 8.
  • the structural unit represented by Chemical Formula 6 may include one or more selected from the group consisting of structural units represented by the following Chemical Formulas 6-1 to 6-3.
  • the structural unit represented by Chemical Formula 7 may include one or more types from the group consisting of the structural units represented by the following Chemical Formulas 7-1 to 7-3.
  • the structural unit represented by Formula 8 may be at least one selected from the group consisting of structural units represented by the following Formulas 8-1 to 8-3.
  • R is a substituted or unsubstituted C 1 to C 3 linear alkyl group or a substituted or unsubstituted C 3 to C 20 branched or cyclic alkyl group, specifically, a substituted or unsubstituted C 1 to C 3 linear alkyl group It may be, and more specifically may be an ethyl group.
  • the airgel precursor may include two or more selected from the group consisting of structural units represented by the formula (2) to (4).
  • the high temperature hydrophobization thermal stability of the airgel, which is the final product may be more excellent.
  • two or more kinds of the structural units may be included, or two or more different structural units may be included.
  • the Xs of the structural units represented by Formulas 2 to 4 may be connected to each other via O. Specifically, it may be represented by one or more selected from the group consisting of structural units represented by the following formulas (9) and (10).
  • X in the structural units represented by Formulas 2 to 4 may be connected to each other through O. Specifically, it may be represented by one or more selected from the group consisting of structural units represented by the following formulas (11) to (13).
  • Si of the structural unit represented by Formula 1 and X or more of the structural units represented by Formulas 9 to 13 in the airgel precursor may be connected to each other via O (oxygen).
  • the airgel precursor is a structural unit represented by the formula (1); And it may include one or more selected from the group consisting of structural units represented by the formula (14) to formula (18).
  • the structural unit represented by Chemical Formula 14 may include one or more types from the group consisting of structural units represented by the following Chemical Formulas 14-1 to 14-3.
  • the structural unit represented by Chemical Formula 15 may include one or more types from the group consisting of structural units represented by the following Chemical Formulas 15-1 to 15-3.
  • the structural unit represented by Chemical Formula 16 may include one or more types from the group consisting of structural units represented by the following Chemical Formulas 16-1 to 16-3.
  • the structural unit represented by Chemical Formula 17 may include one or more types from the group consisting of structural units represented by Chemical Formulas 17-1 to 17-3.
  • the structural unit represented by Chemical Formula 18 may include one or more types from the group consisting of structural units represented by the following Chemical Formulas 18-1 to 18-3.
  • R is a substituted or unsubstituted C 1 to C 3 linear alkyl group or a substituted or unsubstituted C 3 to C 20 branched or cyclic alkyl group, specifically, a substituted or unsubstituted C 1 to C 3 linear alkyl group It may be, and more specifically may be an ethyl group.
  • the structural unit represented by Chemical Formula 1 may be derived from a compound represented by Chemical Formula 21, and the structural unit represented by Chemical Formulas 2 to 4 may be derived from a compound represented by Chemical Formula 22.
  • R, X, R 1 and R 2 are as described in the description of Formula 6-1.
  • R may be an ethyl group
  • X may be Si
  • R 1 may be a methyl group
  • R 2 may be methoxy
  • Hydrolysis degree of the airgel precursor according to an embodiment of the present invention may be 60% to 95%. If the above range is satisfied, the wet gel formed using the same may be formed in a short time. If the degree of hydrolysis is less than the above-mentioned range, the wet gel formation time may be long, and transparency and heat resistance of the airgel may be reduced. When the degree of hydrolysis exceeds the above-mentioned range, durability of the airgel precursor prepared therefrom may be lowered.
  • the airgel precursor according to an embodiment of the present invention is a first step of preparing a mixture by mixing a compound represented by the formula (21) and a compound represented by the following formula 22 with alcohol in a molar ratio of 100: 1 to 100: 20 ; And a second step of hydrolyzing and polycondensing the mixture.
  • R, X, R 1 and R 2 are as described in the description of the above airgel precursor.
  • the alcohol is not particularly limited as long as it is compatible with water and can dissolve the compounds represented by Formulas 21 and 22.
  • the alcohol may be at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol and butanol.
  • the alcohol may be included in an amount of 1 to 40 parts by weight based on 100 parts by weight of the total of the compounds represented by Formulas 21 and 22. If the above range is satisfied, the silica content in the airgel precursor can be appropriately controlled.
  • the second step specifically includes a second step of hydrolyzing the mixture using an acid catalyst and water to form a reactant; And it may include a step 2-2 to prepare an airgel precursor by polycondensing the reactants.
  • the acid catalyst may be at least one selected from the group consisting of hydrochloric acid, nitric acid, acetic acid, citric acid and oxalic acid.
  • the acid catalyst may be included in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the total of the compounds represented by Formulas 21 and 22.
  • the water may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total of the compounds represented by Chemical Formulas 21 and 22, and when the above-mentioned content is satisfied, the degree of hydrolysis is controlled to control the above-described weight average molecular weight and viscosity conditions. It can be prepared an airgel precursor that satisfies.
  • the water and the acid catalyst may be in the form of an acid catalyst aqueous solution.
  • the acid catalyst aqueous solution may be included in the mixture in a dropwise dropwise manner in a dropwise manner.
  • the color may be blurred and the temperature may be higher than room temperature, but the color of the reactant is clear, and the temperature is lowered to room temperature, and then the step 2-2 is performed. Can be done.
  • Step 2-2 may be a step of preparing an airgel precursor by heating and refluxing the reactant at 70 to 100 ° C. for 1 to 30 hours, cooling to room temperature, and filtration under reduced pressure using a filter. When the temperature and time conditions described above are satisfied, an airgel precursor that satisfies the above-described weight average molecular weight and viscosity conditions may be prepared.
  • An airgel according to another embodiment of the present invention may be prepared using an airgel precursor according to an embodiment of the present invention.
  • the airgel according to another embodiment of the present invention is all hydrophobized to small pores in the airgel precursor, it may have excellent hydrophobicity at room temperature and high temperature.
  • the airgel may have high porosity, low thermal conductivity, and excellent mechanical flexibility.
  • the airgel may have a carbon content of 10 to 15% by weight relative to the total weight of the airgel at room temperature, and may have a carbon content of 1 to 4% with respect to the total weight of the airgel at high temperature. That is, due to the high carbon content in the airgel, not only excellent hydrophobicity at room temperature, but also high temperature hydrophobicity may be excellent because more carbon may remain at a higher temperature than a conventional airgel.
  • the airgel may have a specific surface area of 500 m 2 / g to 800 m 2 / g.
  • the aerogel is a porous porous structure comprising a plurality of micropores, nano-sized primary particle particles, specifically, the average particle diameter (D 50 ) of 100 nm or less primary particles are combined to form a mesh It may be formed as a fine structure, that is, a three-dimensional network structure forming a cluster (cluster) of.
  • the carbon content can be measured using Eltra's Carbon / Sulfur Analyzer (CS-800).
  • the specific surface area can be measured by the adsorption / desorption amount of nitrogen according to the partial pressure (0.11 ⁇ p / p0 ⁇ 1) using the ASAP 2020 instrument of Micrometrics.
  • the airgel according to another embodiment of the present invention comprises the steps of preparing a wet gel by adding a base to a silica sol containing an airgel precursor according to an embodiment of the present invention; Aging the wet gel; Surface modification of the matured wet gel; And it can be prepared by a manufacturing method comprising the step of supercritical drying the wet gel.
  • the silica sol may be prepared by further mixing water and alcohol with the airgel precursor. Description of the alcohol is as described above in the description of the airgel precursor.
  • the base examples include inorganic bases such as sodium hydroxide and potassium hydroxide; Or an organic base such as ammonium hydroxide, but in the case of the inorganic base, since the metal ion contained in the compound may be coordinated (coordination) to the Si-OH compound, the organic base may be preferable.
  • the organic base is ammonium hydroxide (NH 4 OH), tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), methylamine, ethylamine, isopropylamine, monoisopropylamine, diethylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, choline, Monoethanolamine, diethanol amine, 2-aminoethanol, 2- (ethyl amino) ethanol, 2- (methyl amino) ethanol, N-methyl diethanolamine, dimethylaminoethanol, diethylaminoethanol, nitrilotriethanol, 2 -(2-aminoethoxy) ethanol, 1-amino-2-propanol, triethanol
  • the base may be precipitated when it is added to the solid phase, it may be preferable to be added in a solution phase diluted with the polar organic solvent described above.
  • the aging step is a process for allowing the wet gel to stand at an appropriate temperature so that the chemical change is completely made, and by the aging process for the wet gel, it is possible to strengthen the network structure inside the wet gel.
  • the moisture inside the wet gel may be substituted with a polar organic solvent during the aging process, and as a result, it is possible to prevent the pore structure deformation and reduction of the silica gel due to evaporation of the moisture inside the wet gel in a subsequent supercritical drying process.
  • the aging step may be carried out until the chemical change in the wet gel is completed, specifically, the wet gel-based composite at 50 to 80 °C 1 hour to 6 hours, more specifically to 60 to 75 °C It can be carried out by immersing in a aging solution for 2 to 4 hours.
  • the aging solution may be alcohol, the description of the alcohol is as described above.
  • the surface deformation may be performed for 1 to 6 hours at 40 to 80 ° C. after the wet gel is immersed in the surface modification solution.
  • the surface modification solution is at least one selected from the group consisting of hexamethyldisilazane, tetramethylchlorosilane, silicone oil, amino silane, alkyl silane, polydimethyl siloxane, and dimethyldichlorosilane and alcohol It may be a solution containing. Description of the alcohol is as described above.
  • the pores of the wet gel may be hydrophobized to facilitate water removal of the pores during supercritical drying.
  • the supercritical drying step may be a supercritical drying step using supercritical carbon dioxide.
  • Carbon dioxide (CO 2 ) is a gaseous state at room temperature and atmospheric pressure, but if it exceeds a certain temperature and high pressure limit called the supercritical point, the evaporation process does not occur, so it becomes a critical state in which gas and liquid cannot be distinguished.
  • Carbon dioxide in the state is called supercritical carbon dioxide.
  • Supercritical carbon dioxide has a molecular density close to a liquid, but has a low viscosity, close to a gas, high diffusion efficiency, high drying efficiency, and short drying time.
  • the surface-modified wet gel may be put in a supercritical drying reactor, and then a solvent replacement process may be performed in which a liquid CO 2 is filled and a solvent inside the silica aerogel is replaced with CO 2 .
  • the temperature is raised to 30 to 80 ° C., preferably 40 to 70 ° C. at a constant temperature increase rate, specifically 0.1 / min to 1 / min, and then the pressure is equal to or higher than the pressure at which carbon dioxide becomes a supercritical state. Maintaining a pressure of 300 bar, preferably 80 to 200 bar, more preferably 100 bar to 150 bar can be maintained for a predetermined time, specifically 20 minutes to 1 hour in the supercritical state of carbon dioxide.
  • carbon dioxide is supercritical at a temperature of 31 ° C. and a pressure of 73.8 bar.
  • the carbon dioxide may be maintained at a constant temperature and a constant pressure for 2 hours to 12 hours, more specifically, 2 hours to 6 hours at which the carbon dioxide becomes a supercritical state, and then the pressure may be gradually removed to complete the supercritical drying step.
  • the airgel according to another embodiment of the present invention comprises the steps of mixing the airgel precursor and the base catalyst according to an embodiment of the present invention to form a wet gel at pH ⁇ 3; Surface modification by mixing with the wet gel and a hydrophobic agent; And it may be prepared by a manufacturing method comprising the step of drying the surface-modified wet gel.
  • the forming of the wet gel is as described in the above-described method for preparing an airgel.
  • the step of modifying the surface by mixing the wet gel and the hydrophobic agent may be a step of silylating the surface of the wet gel using a silylating agent which is a hydrophobic agent.
  • predetermined water in the pores of the wet gel and the used silylating agent can react to form an insoluble compound in water, and water present in the pores by the molar volume of the formed compound. This can be substituted automatically.
  • water and water in the pores of the wet gel may be easily separated from the wet gel by a compound that is insoluble in water. This silylation may not require a separate solvent replacement process.
  • the silylating agent is preferably (R 3 ) 4- n SiCl n , (R 4 ) 4- m Si (OR 5 ) m , (R 6 ) 3 Si-O-Si (R 6 ) 3 , and ( R 7 ) 3 Si-O-Si (R 7 ) 3 It may be one or more selected from the group consisting of, wherein R 3 to R 7 are the same as or different from each other, and each independently, hydrogen, substituted or unsubstituted A C 1 to C 20 linear alkyl group, a substituted or unsubstituted C 3 to C 20 branched or cyclic alkyl group, a substituted or unsubstituted C 5 to C 20 aryl group, n and m are the same as each other Different, and may each independently be 1-4.
  • the silylating agent may be at least one selected from the group consisting of silazane, hexamethyldisilazane, trimethylchlorosilane, hexamethyldisiloxane, trimethylsiloxane and isopropoxytrimethylsilane.
  • the silylating agent may be used in a liquid state or a gaseous state.
  • the liquid state may be a silylating agent alone or a state dissolved in alcohol.
  • the temperature in the step of drying the surface-modified wet gel may be -30 to 200 °C, preferably 0 to 150 °C, the pressure is 0.001 to 20bar, preferably 0.01 to 5bar, more preferably 0.1 to It can be 2 bar and can be dried by radiation, convection and contact drying.
  • the airgel produced by the above-described method for producing an airgel may be 90% or more of the theoretically possible coverage of the inner surface by the organic surface group coated by the surface silylation.
  • coverage means the number of organic surface groups per square nanometer of the inner surface area of the airgel.
  • Surface modification of the porous SiO 2 material with trimethylchlorosilane can theoretically yield coverage of trimethylsilyl groups (TMS) of up to 2.8 nm ⁇ 2 . This can be calculated from the steric bulk of the TMS unit, which is described in the literature as the umbrella effect.
  • the required space from the Si-C (0.189 nm) and CH (0.108 nm) bond lengths and the van der Waals radius of the TMS molecules is estimated to be about 0.36 nm 2 per TMS molecule. In conversion, this corresponds to the coverage of TMS per nm 2 (W. Urbaniak, F. Janowski, B.
  • the coverage can be calculated using the following formula.
  • An airgel blanket according to another embodiment of the present invention may be prepared using an airgel precursor according to an embodiment of the present invention.
  • the airgel blanket according to another embodiment of the present invention is also hydrophobic to all the small pores in the airgel precursor, and thus may have excellent hydrophobicity at room temperature and high temperature.
  • the airgel contained in the airgel blanket may also have high porosity, low thermal conductivity, and excellent mechanical strength.
  • the airgel blanket according to another embodiment of the present invention may be an airgel blanket having excellent thermal insulation having a thermal conductivity of 20 kW / mK or less.
  • the thermal conductivity can be measured using HFM436 Lambda equipment of NETZSCH.
  • the airgel blanket according to another embodiment of the present invention after immersing the substrate for the blanket in a silica sol containing the airgel precursor according to an embodiment of the present invention, by adding a base to prepare a wet gel-based composite Making; Aging the wet gel-based composite; Surface modifying the aged wet gel-based composite; And it may be prepared by a manufacturing method comprising the step of supercritical drying the wet gel-based composite.
  • the blanket substrate may be a film, a sheet, a net, a fiber, a porous body, a foam, a nonwoven fabric, or a laminate of two or more thereof.
  • the surface roughness may be formed or patterned.
  • the blanket substrate may be a fiber capable of further improving the thermal insulation performance by including a space or a space in which an airgel is easily inserted into the blanket substrate.
  • the blanket base material may have a low thermal conductivity.
  • the blanket base material may be polyamide, polybenzimidazole, polyaramid, acrylic resin, phenol resin, polyester, polyether ether ketone (PEEK), polyolefin (for example, polyethylene, polypropylene, or copolymers thereof). Etc.), cellulose, carbon, cotton, wool, hemp, nonwoven fabric, glass fiber or ceramic wool, and the like, but are not limited thereto. More specifically, the substrate may include glass fiber or polyethylene.
  • Tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS) and ethanol (C 2 H 5 OH) (industrial, 94-96% by volume) at room temperature (23 ⁇ 3 °C) in the amounts shown in Table 1
  • the first reactant was prepared by dropwise dropwise addition of an aqueous hydrochloric acid solution of PH 1.0 dropwise for 1 hour while stirring at a speed of 130 rpm for 1 hour.
  • the reaction was terminated and cooled to room temperature to prepare a second reactant.
  • the second reactant was filtered under reduced pressure using a filter to prepare an airgel precursor having a molar ratio and weight molecular weight of the TEOS-derived structural unit and MTMS-derived structural unit shown in Table 1.
  • Viscosity measuring method It measured at 100 rpm and 20 degreeC using Viscometer TV-22 (Disk Type, TOKISANGYO Co. LTD).
  • the airgel precursor of Synthesis Example 4 was confirmed to maintain a relatively constant viscosity even when heated at 50 °C for 24 hours. From these results, it can be inferred that the airgel precursor of Synthesis Example 4 according to the present invention can maintain a constant viscosity even after 6 months at room temperature and has excellent durability.
  • the airgel precursor, ethanol and water of Synthesis Example 1 to Synthesis Example 4 and Comparative Synthesis Example 1 shown in Table 2 were mixed at a weight ratio of 1: 0.5: 0.3 to prepare an airgel precursor solution.
  • the wet gel was aged at 60 ° C. for 1 hour.
  • the gel was subjected to supercritical drying for 8 hours using CO 2 at 50 ° C. and 100 bar, and dried for 1 hour at 150 ° C. and atmospheric pressure to prepare an airgel.
  • An airgel was prepared in the same manner as in Example 4 except that surface modification was not performed.
  • An airgel precursor solution of Synthesis Example 4 was mixed with ethanol and water in a weight ratio of 1: 0.5: 0.3 to prepare an airgel precursor solution.
  • the wet gel was aged at 60 ° C. for 1 hour.
  • the aged wet gel was acidified with an aqueous hydrochloric acid solution, hexamethyldisiloxane and ethanol were added thereto, and stirred at room temperature for 5 hours to separate the aqueous phase. Stir at room temperature for 24 hours, and separate the aqueous phase.
  • the mixture was stirred for 3 days at room temperature, and the aqueous phase was separated three times.
  • the gel was dried in a hot nitrogen stream for 1 hour to prepare an aerogel.
  • the wet gel was prepared by naturally gelling the airgel precursor prepared in Comparative Synthesis Example 2.
  • the wet gel was aged at 60 ° C. for 24 hours.
  • the aged wet gel was subjected to supercritical drying for 8 hours using CO 2 at 50 ° C. and 100 bar, and dried for 1 hour at 150 ° C. and atmospheric pressure to prepare an airgel.
  • the pore distribution in the airgel of Example 5 and Comparative Example 3 was measured and the results are shown in FIG. 2.
  • the x-axis denotes pore diameter (unit: mm)
  • the y-axis denotes pore volume (cm 3 / g).
  • the pores in the airgel of Example 5 were found to have a uniform diameter and volume compared to the pores in the airgel of Comparative Example 3.
  • Example 1 10.3 2.5 75.72
  • Example 2 11.4 2.7 76.31
  • Example 3 12.2 3.3 72.95
  • Example 4 12.9 3.6 72.09
  • Example 5 3.9 1.1 71.79 Comparative Example 1 8.0 0.5 93.75 Comparative Example 3 2.5 0.6 76.00
  • the airgel of Example 5 used the same airgel precursor as that of Example 4, except that only the surface modification process was not performed. Since the airgel of Example 5 had a carbon reduction rate of 71.79% after heating, it was confirmed that the high temperature stability was the best.
  • Comparative Example 1 was not hydrophobized because the airgel precursor, even if the airgel was prepared under the same conditions as the embodiment was not superior to the room temperature hydrophobicity compared to the examples. In addition, after heating, the carbon content was reduced by 93.75% and the carbon content reached 0.5%. From these results, it was confirmed that Comparative Example 1 was not excellent in high-temperature hydrophobicity and poor in high temperature stability.
  • an airgel was prepared using an aerogel precursor using TEOS and MTMS in the same molar ratio as in Example 4, except that the airgel precursor prepared by the acid catalyst condensation reaction was different from the hydrolysis and polycondensation reactions. there was.
  • An airgel precursor solution of Synthesis Example 4 was mixed with ethanol and water in a weight ratio of 1: 0.5: 0.3 to prepare an airgel precursor solution.
  • the wet gel-based composite was aged at 60 ° C. for 1 hour.
  • the aged wet gel-based composite was surface modified at 60 ° C. for 4 hours.
  • the surface-modified wet gel-based composite was subjected to supercritical drying for 8 hours using CO 2 at 50 ° C. and 100 bar, and dried for 1 hour at 150 ° C. and atmospheric pressure to prepare an airgel blanket.
  • An airgel blanket was prepared in the same manner as in Example 7, except that surface modification was not performed.
  • a glass gel was deposited on the airgel precursor prepared in Comparative Synthesis Example 2, followed by natural gelation to prepare a wet gel-based composite.
  • the wet gel-based composite was aged at 60 ° C. for 1 hour.
  • the aged wet gel-based composite was surface modified at 60 ° C. for 4 hours.
  • the surface-modified wet gel-based composite was subjected to supercritical drying for 8 hours using CO 2 at 50 ° C. and 100 bar, and dried for 1 hour at 150 ° C. and atmospheric pressure to prepare an airgel blanket.
  • An airgel blanket was prepared in the same manner as in Comparative Example 4 except that surface modification was not performed.
  • Insulation evaluation method Measured by using NETZSCH HFM436 Lambda equipment.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne : un précurseur d'aérogel, qui comprend, dans un rapport molaire de 100 : 1 à 100 : 20, une unité structurale représentée par la formule chimique 1 suivante, et un ou plusieurs éléments choisis dans le groupe constitué d'unités structurales représentées par les formules chimiques suivantes 2-4, a un poids moléculaire moyen en poids de 1 000 à 6 000 g/mol, et a une viscosité de 2,0-4,0 cps après avoir été chauffé à 45-60 °C pendant 24 heures ou plus; un procédé de préparation associé; un aérogel préparé à partir de celui-ci; et un procédé de préparation d'aérogel l'utilisant.
PCT/KR2017/008650 2016-08-09 2017-08-09 Précurseur d'aérogel, son procédé de préparation, aérogel préparé à partir de celui-ci, et procédé de préparation d'aérogel l'utilisant WO2018030796A1 (fr)

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JP2019501896A JP6672524B2 (ja) 2016-08-09 2017-08-09 エアロゲル前駆体、その製造方法、これにより製造されたエアロゲルおよびこれを用いたエアロゲルの製造方法
US15/772,681 US10773964B2 (en) 2016-08-09 2017-08-09 Aerogel precursor, method for preparing the same, aerogel prepared therewith, and method for preparing aerogel using the same
EP17839814.5A EP3357927B1 (fr) 2016-08-09 2017-08-09 Précurseur d'aérogel, son procédé de préparation et procédé de préparation d'aérogel l'utilisant
CN201780004155.4A CN108368135B (zh) 2016-08-09 2017-08-09 气凝胶前体、该气凝胶前体的制备方法、用其制备的气凝胶、和用其制备气凝胶的方法

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