CN113563012B - Preparation method of cold-resisting and heat-insulating hydrophobic aerogel composite jelly and related product thereof - Google Patents

Preparation method of cold-resisting and heat-insulating hydrophobic aerogel composite jelly and related product thereof Download PDF

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CN113563012B
CN113563012B CN202010354893.5A CN202010354893A CN113563012B CN 113563012 B CN113563012 B CN 113563012B CN 202010354893 A CN202010354893 A CN 202010354893A CN 113563012 B CN113563012 B CN 113563012B
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aerogel
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water
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temperature
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CN113563012A (en
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陈建宏
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Taiwan Aerogel Technology Material Co Ltd
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Abstract

The preparation method of the hydrophobic aerogel composite jelly comprises the following steps: (S1) a mixing step; (2) a hydrolysis step; (3) a condensation step; (4) an aging step; (5) a high-temperature pulse water washing step; (6) a drying step; and (7) a compounding step. The hydrophobic aerogel composite jelly is a high-viscosity jelly formed by mixing and stirring the prepared hydrophobic aerogel mixed with inorganic fibers and inorganic glue, and the developed product has the advantages of excellent cold-resisting and heat-insulating properties, proper strength, light weight, good flame retardance, good water repellency and the like.

Description

Preparation method of cold-resisting and heat-insulating hydrophobic aerogel composite jelly and related product thereof
Technical Field
The invention relates to a preparation method of a cold-resisting and heat-insulating hydrophobic aerogel composite jelly and a related product thereof, the composite jelly has the properties of cold resistance, low temperature resistance, heat insulation and water repellency, and particularly relates to a preparation method of an aerogel composite jelly and a related product thereof, and the composite jelly can resist a high temperature and a low temperature range from-200 ℃ to 300 ℃.
Background
Aerogel is a porous material with three-dimensional net structure and has low density (0.003-0.2 g/cm) 3 ) High specific surface area (500 to 2,000m) 2 (g) and low thermal conductivity (0.02-0.036 w/mK). The porosity can reach more than 95%, and the aerogel contains a large amount of air, so that the aerogel is transparent in appearance, has low heat transfer coefficient, low bass transfer rate, low dielectric constant and the like, and has excellent heat insulation, sound insulation, electric insulation, high adsorption and high-efficiency filtration properties. However, in practice, in order to achieve the above functions, the aerogel should be uniformly dispersed on the substrate such as rock wool, glass fiber or carbon fiber to form the aerogel heat insulation blanket. At present common aerogel thermal-insulated blanket has to fall whitewashed easily and under-200 ℃ to 300 ℃ temperature interval used repeatedly, makes the hydrone permeate the thermal-insulated blanket of aerogel and form the ice-cube in the blanket when being close to freezing point temperature easily, therefore leads to laying the pipeline of the thermal-insulated blanket of aerogel and rusts or destroy thermal-insulated blanket structure. In addition, the conventional aerogel thermal insulation blanket is formed by bonding the aerogel powder with a common organic adhesive, so that the organic adhesive can crack at a temperature higher than 300 ℃ and release a large amount of toxic gas or odor, and the aerogel thermal insulation blanket can crack obviously to reduce the thermal insulation effect. All the above phenomena are easy to cause corrosion of the pipeline configured by the aerogel thermal insulation blanket and harm to personnel or environment. Therefore, there is a need for innovative low-temperature heat-insulating products that have superior heat-insulating properties and do not cause fire at high temperatures in the oceangoing fishery industry, fresh food transportation industry, and low-temperature manufacturing industry.
The conventional aerogel preparation method is based on sol-gel synthesis, and mainly comprises mixing precursors such as silane oxide (alkoxysilane), methyl orthosilicate, or water glass, etc. with an organic solvent, and then adding an acid catalyst to perform hydrolysis reaction (hydrolysis). After a period of hydrolysis, an alkali catalyst is added to carry out condensation reaction (condensation), and sol is gradually formed in the condensation process. The molecules in the sol are continuously bonded to form a semi-solid polymer gel gradually. After a period of curing (aging), the sol forms a three-dimensional network structure with stable structure. And finally, carrying out solvent replacement by using solvents such as n-butyl alcohol, n-hexyl alcohol, n-hexane or cyclohexane, and the like, and extracting and drying the solvent in the three-dimensional network structure by using a supercritical drying technology to obtain porous dry hydrophobic aerogel powder.
The preparation method of the hydrophobic aerogel is also based on sol-gel synthesis, and mainly comprises mixing precursors of alkylene siloxane compounds (such as methyltrimethoxysilane (MTMS) or Methyltriethoxysilane (MTES)) and the like with an organic solvent, and then adding an acid catalyst for hydrolysis reaction. After a period of hydrolysis, a condensation reaction takes place and a gel is gradually formed during the condensation. And then, carrying out solvent replacement by using solvents such as n-butyl alcohol, n-hexyl alcohol, n-hexane or cyclohexane and the like, and drying at normal temperature and normal pressure or at high temperature and normal pressure after the solvent replacement is finished. Alternatively, a silane-oxygen compound (e.g., tetraethoxysilane (TEOS) or Tetramethoxysilane (TMOS)) precursor may be mixed with an organic solvent, followed by hydrolysis reaction with the addition of an acid catalyst. After a period of hydrolysis, alkali catalyst is added for condensation reaction, and a stable three-dimensional network structure is gradually formed in the condensation process. Finally, solvent replacement is carried out by using solvents such as n-butyl alcohol, n-hexyl alcohol, n-hexane or cyclohexane, and then hydrophobic modification is carried out by using modified materials such as trimethylchlorosilane or hydrophobic silane, so that the hydrophobic functional group structure is chemically bonded with the three-dimensional network structure. Finally, the solvent in the aerogel is dried by using an atmospheric pressure drying technology to obtain a porous dry aerogel block.
Chinese patent publication No. CN101679657B mentions aerogel particles and methods of making the same, specifically disclosing aerogel particles having an average particle size of less than 1 micron, articles containing the aerogel particles, methods of making the aerogel particles, and uses of the aerogel particles. According to the disclosed manufacturing method, the aerogel starting particles are homogenized or wet milled and may be surface treated during the milling process to prevent agglomeration or aggregation. The aerogel particles obtained had the following characteristics: (1) silica-containing glue particles; (2) at least 80% have a particle size of less than 1 micron; (3) an average particle size of 0.1 to 1 micron; and (4) hydrophobic in nature. The preparation of such hydrophobic aerogel particles requires homogenization or wet milling of the aerogel by a milling process, which is not easy to handle and cost effective.
Chinese patent publication No. CN104556969A mentions a preparation method of a hydrophobic silica aerogel heat insulation composite material, which specifically comprises the following steps: (1) preparation of silica sol: adding organic solvent, water and acid catalyst into siloxane as a precursor to obtain silicon dioxide sol; (2) preparation of composite gel: adding a flame retardant and an infrared blocking agent into the silica sol, uniformly stirring, adding an alkali catalyst, and immersing the inorganic fiber product into the silica sol for standing; (3) solvent replacement: replacing the composite gel with an organic solvent; and (4) drying: drying the composite gel. In detail, in this prior art, an inorganic fiber product is dipped into a silica sol and left to stand at 0 to 80 ℃ for 0.01 to 72 hours to obtain a composite gel, followed by aging at 0 to 80 ℃ for 0 to 96 hours; the aged composite gel is then displaced with an organic solvent for about 1 to 48 hours, times 1 to 10 times. The above-mentioned lengthy overall process does not correspond to economic cost.
Chinese patent publication No. CN105753388a mentions aerogel compositions and methods of making and using the same, where the compositions include aerogel components and have low thermal conductivity. Further, a method of preparing a slurry or composite material, comprising: combining about 60 to 95vol% of an aerogel component, an inorganic binder selected from cement, gypsum, lime, or any combination thereof, and a surfactant. Further, the resulting composition after drying is a self-supporting rigid composite and has a thermal conductivity of less than about 20 mW/mK. In the prior art, the aerogel is hydrophobic, the hydrophobic aerogel is difficult to be uniformly mixed with inorganic binders such as cement, gypsum or lime, and the hydrophobic aerogel has the defects that the aerogel is rapidly cracked and generates toxic smoke at high temperature above 350 ℃.
Japanese patent laid-open No. JP200835648 describes a porous material and a process for producing the same, which comprises mixing an organic solvent with a silane oxide compound (e.g., TEOS) or a silicate compound (e.g., water glass) to synthesize a sol-gel and modifying the sol-gel with a modifier to obtain a porous material, whereby the hydrophilic functional groups on the surface of the porous material are replaced with hydrophobic functional groups, so that the aerogel can be prevented from being broken by the influence of the surface tension of water and dried at room temperature and under normal pressure.
Chinese patent publication No. CN105025598A proposes an electrothermal composite ceramic tile and a preparation method thereof, wherein an electrothermal film is used as a heating component, and the composition of the electrothermal composite ceramic tile contains 55 to 75wt% of organic adhesive, such as: epoxy resin, polyurethane resin or modified silicone resin, etc., but these organic substances are liable to release toxic gases during heating.
At present, the cold-resisting and heat-insulating products in the market mainly utilize organic foaming sponge or foaming sponge tubes, and the porous foaming materials are porous plastic structures prepared by foaming organic plastic materials. Although the porous organic foam sponge has light weight and good heat insulation effect by using the foaming technology, and the heat conductivity is about 0.04 to 0.06W/mK, the disadvantage is that the use temperature is below 150 ℃, and the sponge can be rapidly cracked at high temperature and generates toxic dense smoke. On the other hand, the use of water molecules at low temperatures causes condensation inside the foamed sponge, resulting in loss of the heat insulation effect and severe corrosion of the internal pipe provided with the sponge.
In addition, a few foamed porous ceramic materials are applied to the range of low temperature of-100 ℃ to high temperature of 300 ℃ for recycling, and the prepared porous ceramic plates are mainly foamed ceramics, honeycomb ceramics or granular ceramic knots and are all silicate ceramic materials fired at high temperature. The porous ceramic plate has a high-density ceramic structure, and has light weight, thin thickness and good flame retardant property by using a foaming technology. However, in a low temperature water molecule condensation environment, a large amount of water is accumulated inside the foamed porous ceramic material, thereby degrading the heat insulation property. Most importantly, once a large amount of moisture is accumulated in the porous ceramic, the porous ceramic is burst to affect the safety of a factory once the porous ceramic is rapidly heated to a high-temperature environment, and the internal metal pipeline is continuously corroded to cause pipeline damage, so that the phenomena easily cause the leakage of raw materials in the operation of the pipeline or the safety accidents such as explosion and the like.
Disclosure of Invention
One object of the present invention is to improve the disadvantages associated with conventional aerogel insulation blankets, such as the disadvantages associated with their use and environmental pollution.
Another objective of the present invention is to provide an aerogel composite gel material obtained by mixing silica aerogel material with high thermal insulation and low cracking under flame with inorganic fiber, inorganic glue solution and a very small amount of water-repellent agent, and drying the gel material to obtain an aerogel thermal insulation board or thermal insulation brick with super water-repellent and high thermal insulation.
Another objective of the present invention is to improve the problem that the currently used organic foamed sponge or foamed sponge tube can be cracked rapidly at a high temperature of 200 ℃ and generate toxic dense smoke to harm the production line and personnel. In addition, the problem of serious corrosion of internal pipelines caused by the phenomenon of water dripping accumulated by the organic foaming sponge in a low-temperature environment can be solved.
Still another objective of the present invention is to improve the problem that the current aerogel thermal insulation blanket cannot be applied to high temperature environment. In addition, the related heat insulation blanket product prepared by the current hydrophobic aerogel has the problems of thermal cracking, pulverization and the like of the internal hydrophobic aerogel and related organic substances at the high temperature of 300 ℃.
It is another object of the present invention to replace solvent replacement, hydrophobic modification and expensive supercritical drying techniques in conventional hydrophobic aerogel production in the aerogel production process to produce hydrophobic aerogels. Specifically, the pulse water washing technology is only needed to be used for a short time in the preparation of the hydrophobic aerogel so as to prepare the aerogel product, thereby reducing the manufacturing cost and improving the yield.
The present invention also provides a method for preparing aerogel composite glue, which can be used to directly coat the aerogel composite glue on various metals, ceramics, wood and plastics by using conventional spraying, pressing or gluing techniques, so as to improve the convenience of subsequent processing and operation.
It is another objective of the present invention that the aerogel composite gel prepared can be sprayed, pressed or glued on general inorganic fiber cloth or fiber blanket, such as: the glass fiber, ceramic fiber, rock wool fiber and carbon fiber are combined to obtain the aerogel heat insulation blanket with flexibility, water repellency and heat insulation property, so as to be applied to indoor and outdoor heat insulation.
The invention provides a hydrophobic aerogel composite glue material which is formed by uniformly mixing super-hydrophobic aerogel, inorganic fibers, an inorganic glue solution, a small amount of dispersant and other materials by combining technologies such as siloxane compound mixing, sol-gel synthesis and the like, so that the hydrophobic aerogel composite glue material contains hydrophobic aerogel and hydrophilic inorganic fibers which are uniformly mixed, and has excellent heat insulation and flame retardant properties. The preparation method provided by the invention comprises the following steps: (1) a mixing step: adding the siloxane mixture into the mixed solvent to disperse the siloxane mixture in the mixed solvent to form a uniform mixed solution; (2) a hydrolysis step: adding an acid catalyst into the mixed solution for hydrolysis reaction; (3) condensation step: adding an alkali catalyst into the hydrolyzed mixed solution for condensation reaction, adding a large amount of dispersion solvent in the condensation reaction, emulsifying and dispersing to form stable liquid drops in the condensation solution and form a stable wet glue structure with the particle size between sub-micron and micron grade in the dispersion solvent; (4) an aging step: aging the wet glue structure in a specific temperature range to promote the molecules which are not combined with each other to form a net structure in the wet glue structure to be further combined with each other to form a more stable wet glue structure; (5) high-temperature pulse water washing: under the conditions of normal pressure and high temperature, a large amount of pulse water is used for washing to quickly replace the solvent in the wet glue until the wet glue is milky and transparent; (6) a drying step: evaporating and drying the solvent of the wet glue at normal pressure, and quickly separating water molecules in a wet glue structure by utilizing the environment of about 80-90 ℃ in the drying process to obtain hydrophobic aerogel particles with heat insulation property; and (7) compounding: mixing aerogel particles obtained by evaporating and drying a solvent and inorganic fibers in a stirrer to form an evenly-dispersed inorganic mixture, adding an inorganic glue solution to enable the aerogel particles, the inorganic fibers and the inorganic glue solution to interact into aerogel composite jelly with viscosity, and adding one or more of water, a viscosity agent, a dispersing agent, a water drawing agent and aerogel powder to adjust the viscosity of the jelly. In the obtained jelly, the content of the hydrophobic aerogel particles is between 35 and 50v/v%, the content of the inorganic fibers is between 10 and 25v/v%, and the content of the inorganic glue solution and the dispersing agent is between 35 and 55v/v%. The gel-like mass is dried to provide an aerogel insulation panel having a total aerogel and inorganic fiber content of about 75 to 95 weight percent.
Further, the siloxane based mixture comprises one or more selected from the group consisting of: siloxane compounds (alkoxysilanes), alkylene siloxane compounds, and R-based-silica-gel oligo-molecules. Among these, silicone compounds, such as: tetramethoxysilane (TMOS) or Tetraethoxysilane (TEOS), which herein primarily provide aerogel network bond density for increased structural strength; alkylene siloxane compounds, such as: methyltrimethoxysilane (MTMS) or Methyltriethoxysilane (MTES), which herein primarily provide aerogel hydrophobic properties to increase flexibility and thus environmental stability of the aerogel structure; or R-group-silica gel oligo molecules, such as: polydimethylsiloxane (PDMS) or silica gel precursors (DMDMS), which mainly provide elasticity and flexibility to the aerogel and thus improve the environmental stability of the aerogel structure, where the R group is a functional group connected to the end of the silica gel oligo-molecular chain.
Further, the mixed solvent comprises a first component and a second component, the first component comprising one or more selected from the group consisting of: water, alcohols, aromatics, and alkanes, the second component comprising one or more selected from the group consisting of: emulsifier and surfactant.
Further, the acid catalyst for hydrolysis comprises one or more components selected from the group consisting of: sulfuric acid, phosphoric acid, nitric acid and boric acid.
Further, the surfactant in the mixed solvent comprises one or more selected from the group consisting of: cationic surfactants, anionic surfactants, zwitterionic surfactants, and nonionic surfactants.
Further, the base catalyst for condensation comprises one or more components selected from the group consisting of: sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium bicarbonate.
Furthermore, the solvent used in the condensation step may be an aqueous solution or a mixed solvent prepared by blending a hydrophilic solvent and a hydrophobic solvent according to the process requirements. During the condensation reaction, large amount of dispersing solvent (such as water, secondary water, alcohol, aromatic compound, alkane or their mixture) is added to make the mixed solution gel fast to form wet glue and produce large amount of pores. The blending ratio of the hydrophilic solvent and the hydrophobic solvent is utilized to control the interaction of the dispersion solvent and the mixed solution, and further control the microphase separation and gelation phenomena of the formed liquid drops in the aggregation and combination process, thereby controlling the characteristics of the formed wet glue molecules such as particle size, pore distribution and the like.
Further, in the high-temperature pulse water washing step, a 50-95 ℃ high-temperature pulse water washing device is used for carrying out the water washing procedure of the aerogel wet glue particles, on one hand, the device provides 50-95 ℃ high-temperature water for carrying out rapid replacement with organic components or solvents in the wet glue structure, wherein the higher the temperature is, the faster the replacement rate is; on the other hand, the pulse wave acting force is utilized to accelerate the high-temperature water to permeate into the wet glue so as to improve the replacement efficiency of the organic components or the solvent. Therefore, the high-temperature pulse water washing device can obviously improve the water washing replacement effect of the organic components or the solvent in the stable wet glue structure so as to reduce the whole process time. The high-temperature pulse water washing step can improve the solvent replacement water washing efficiency of the wet glue by about 30 to 70 percent by utilizing the high temperature and pulse wave effect. Taking wet glue with the particle size of 2mm as an example, the washing time can be completed within about 10 minutes, so that water and organic components or solvents in the wet glue structure are replaced until the wet glue is completely clean.
Further, the drying is carried out by a general high-temperature normal-pressure method. Drying to obtain aerogel particles with water repellency and heat insulation properties. Overall, the process can be completed in less than 24 to 30 hours and the aerogel particles having hydrophobicity can be continuously produced, thereby increasing the production efficiency.
Further, the hydrophobic aerogel granule that prepares can be directly with inorganic fiber under the mixer stirring power intermix form evenly dispersed aerogel/inorganic fiber mixture, add inorganic glue solution again afterwards and stir and make inorganic adhesive disperse in aerogel and inorganic fiber surface evenly, impel aerogel granule, inorganic fiber and inorganic adhesive interact become the compound jelly of viscidity form aerogel, add water, viscidity agent, dispersant, drawing agent or the nature of aerogel powder adjustment jelly afterwards, can obtain the finished product. The aerogel content in the aerogel composite jelly is between 35 and 50v/v%, the inorganic fiber content is between 10 and 25v/v%, and the inorganic glue solution content is between 35 and 55v/v%. The aerogel composite jelly has high adhesiveness, and can be directly filled or coated on a metal pipeline or a refrigerator of ultralow-temperature equipment or can be prepared into products such as high-water-repellency aerogel/inorganic fiber composite bricks or plates by a die-casting forming method.
Furthermore, after the composite jelly is dried, the content of the aerogel and the inorganic fiber accounts for 75 to 95 weight percent, the composite jelly has excellent adhesion with materials such as metal or ceramics under the environment of low temperature to-200 ℃, and the heat transfer coefficient at room temperature is 0.04 to 0.045W/mK.
Further, the inorganic fiber is one or more materials selected from the group consisting of: ceramic fibers, glass fibers, carbon fibers, oxidized fibers, rock wool fibers, and metal oxide fibers.
Furthermore, the aerogel composite jelly can be directly added to a fiber blanket or foamed plastic by processing technologies such as coating, pressure absorption or extrusion filling, so that a large amount of high water-repellent aerogel/inorganic fiber composite jelly is filled in the fiber blanket or foamed plastic, and then a plastic film is used for sealing the film, so that the high water-repellent aerogel composite heat insulation blanket or the high water-repellent aerogel composite structure can be manufactured. The fibrous blanket may be one or more materials selected from the group consisting of: organic non-woven fabrics, glass fiber blankets, carbon fiber blankets, and rock wool blankets.
Further, the organic nonwoven is one or more members selected from the group consisting of: polyester fiber nonwoven fabrics, polyolefin fiber nonwoven fabrics, and nylon fiber nonwoven fabrics.
Further, the foamed plastic is one or more selected from the group consisting of: polyester foam materials, polyolefin foam materials, polyamide foam materials, polyurethane foam materials, polycyanate foam materials and polyurea foam materials.
The invention has the following effects:
1. in the condensation step, hydrophilic solvents and hydrophobic solvents with different proportions are mixed to generate a hydrophilic-hydrophobic mixed solvent effect, so that the mixed solution reduces the hydration of water molecules and silica molecules in the gelation process, and the shrinkage of a wet gel structure in the drying process can be obviously avoided, thereby producing the hydrophobic aerogel particles with high porosity. Therefore, the heat insulation and cold resistance performance of the hydrophobic aerogel can be obviously improved, the content of aerogel particles in the mixed material can be obviously improved, and the practical value is improved.
2. The density, particle size, porosity and pore size of the obtained hydrophobic aerogel particles can be regulated and controlled according to preparation conditions (the content of siloxane compounds, the content of olefin-based siloxane compounds, the content of R-based-silica gel micromolecules, the content of solvents, the viscosity of the solvents, the content of acid catalysts, the content of alkali catalysts, the components and the content of dispersion solvents, the pulse washing temperature and the stirring speed.
3. In the condensation step, a large amount of aqueous solution is crushed and rapidly stirred, and then the aqueous solution is dried to remove, so that the hydrophobic aerogel particles with the particle size ranging from hundreds of micrometers to tens of millimeters can be produced. The hydrophobic wet glue produced by the method can be mixed in common base materials in high content under the condition of water content, and high porosity can be kept in the base materials, so that the heat insulation and cold resistance properties of various base materials are improved.
4. By controlling the conditions of pulse acting force, water temperature and the like of high-temperature pulse washing, the solvent replacement time of the whole wet glue can be shortened, and the preparation of a large amount of hydrophobic aerogel particles can be finished within 8 to 24 hours at the fastest speed, so that the production efficiency is improved.
5. The prepared hydrophobic aerogel particles can be mixed with inorganic fibers and an inorganic glue solution to form uniformly dispersed viscous aerogel composite jelly, and then one or more of water, a viscosity agent, a dispersing agent, a water drawing agent and aerogel powder are added to adjust the property of the composite jelly, so that the composite jelly can be directly filled or coated on a metal pipeline or a refrigerator of extremely low temperature equipment to provide the characteristics of ultra-water drawing and low temperature resistance.
6. The prepared high water-repellent aerogel/inorganic fiber composite jelly can resist the high temperature of 200 ℃ below zero to 300 ℃ and has excellent low-temperature cold-resisting and high-temperature heat-insulating properties, and the heat transfer coefficient is 0.035 to 0.042W/mK at room temperature, thereby providing industrial application. Specifically, the fiber blanket or the foam material can be directly filled by coating, pressure absorbing or extrusion filling, and the like, and then the plastic film is used for sealing the film to prepare the high-water-repellency heat insulation blanket or the high-water-repellency composite foam material, so that the high-water-repellency heat insulation blanket or the high-water-repellency composite foam material can be directly applied to pipeline coating.
Drawings
Fig. 1 is a schematic view of a preparation process of the cold-resisting and heat-insulating hydrophobic aerogel composite material according to the embodiment of the present invention.
FIG. 2 is a photograph showing the appearance of submicron hydrophobic aerogel particles prepared according to the present invention.
FIG. 3 is a photograph showing the appearance of several millimeters of hydrophobic aerogel particles prepared according to the present invention.
Fig. 4 (a) to 4 (C) are scanning electron microscope photographs of several millimeters of hydrophobic aerogel particles prepared according to the present invention, taken at different magnifications.
FIG. 5 is a photograph of the cold-resistant, heat-insulating, and water-repellent aerogel bricks produced according to the present invention floating on the water.
FIG. 6 is a photograph of a cold-resistant, heat-insulating, water-repellent aerogel block made according to the present invention cut to a volume of 10.5 cm x7.8 cm.
Fig. 7 is a photograph of the interface angle of water drops of the cold-resistant, heat-insulating, and water-repellent aerogel brick prepared according to the present invention.
Detailed Description
Referring to fig. 1, a method for preparing a hydrophobic aerogel composite gel with super water repellency, cold resistance and thermal insulation according to an embodiment of the present invention is disclosed, which comprises the following steps: the preparation method comprises a mixing step (S1), a hydrolysis step (S2), a condensation dispersion step (S3) or a condensation crushing step (S3'), an aging step (S4), a high-temperature pulse water washing step (S5), a drying step (S6) and a compounding step (S7), wherein hydrophobic aerogel particles of hundreds of micrometers to several millimeters prepared by the method can be used for preparing hydrophobic aerogel compound jelly with super water repellency, cold resistance and heat insulation, and further preparing the aerogel compound brick with super water repellency, low temperature resistance, cold resistance and heat insulation.
Mixing step (S1): and stirring and mixing the siloxane compound, the alkylene siloxane compound and one of the R-group-silica gel micromolecules or the mixture thereof with the mixed solvent to form a mixed solution. Among them, siloxane compounds such as tetramethoxysilane or tetraethoxysilane; alkylene siloxane compounds such as methyltrimethoxysilane (MTMS) or Methyltriethoxysilane (MTES); r group-silica gel oligo molecule such as polydimethyl silica gel (PDMS) or silica gel precursor (DMDMDMS), wherein R group is a functional group connected to the end of silica gel molecular chain and containing acid group-COOH or amino group-NH 2 Or imino-NH-or polyamino-NH 2 Or hydroxy-OH or epoxy-COH or isocyanato-N = C = O or isocyanato-N-CO-N-, and the number of carbons in the functional group is from C1 to C6. The total content of the alkenyl siloxane compound and the R-based-silica gel oligomer is 3.0mol% to 40.0mol% and the content of the mixed solvent is 97.0mol% to 60.0mol% based on the total content of the mixed solution.
The mixed solvent used in the mixing step (S1) comprises a first component and a second component, the first component being one or more selected from the group consisting of: water, alcohols, aromatics and alkanes, the second component being one or more selected from the group consisting of: emulsifiers or surfactants, and the like. Specifically, alcohols such as ethanol, aromatic species such as toluene, alkanes such as cyclohexane, emulsifiers such as polyvinyl alcohol, and surfactants such as cetyltrimethylammonium chloride (CTAC).
In the mixed solvent, a surfactant is added for the purpose of reducing the interfacial tension of water molecules, and the surfactant may comprise one or more selected from the group consisting of: cationic surfactants, anionic surfactants, zwitterionic surfactants, nonionic surfactants, and the like.
Hydrolysis step (S2): adding an acid catalyst into the mixed solution to perform a hydrolysis reaction. The ratio of the total content of the alkenyl siloxane compound and the R-based-silica oligo to the content of the acid catalyst is 1.
Condensation dispersion (S3) or condensation fragmentation step (S3'): adding an alkali catalyst into the mixed solution to perform condensation reaction. During the condensation reaction, a large amount of dispersing solvent (such as one or more of water, secondary water, alcohols, aromatics and alkanes) is added, and the dispersing solvent can promote the mixed solution to be rapidly gelatinized and generate a wet glue structure with a large number of holes. The molar ratio of the acid catalyst to the base catalyst is, for example, 1:1 to 1:4. The used dispersion solvent can be aqueous solution or mixed solvent prepared by blending hydrophilic solvent and hydrophobic solvent according to the process requirement.
In the condensation-dispersion step (S3), before the condensation reaction is completed, the dispersion medium makes the mixed solution form a solution-like sol (solution-like sol) and the solution-like sol is dispersed into hundreds of nano-particles wet sol under the effect of stirring force and suspended in the dispersion medium by stirring in the hydrophilic dispersion medium of the mass of incompatible system at a fast speed of 600rpm to 2000 rpm. The volume ratio of the mixed solution to the dispersion solvent is 1.5 to 1:4. Moreover, the higher the content of the dispersion solvent, the lower the agglomeration behavior of the wet glue; the higher the base content of the dispersion vehicle, the more severe the macrophase separation behavior and the opaque appearance of the wet gum, but the higher the porosity of the structure and the lower the density.
In the step of condensation and fragmentation (S30), before the completion of the condensation reaction, the dispersion medium causes the mixed solution to form a sol in a solution form, and the sol is allowed to stand in a large amount of aqueous dispersion medium of an incompatible system for gel solidification, so that silicon molecules in the mixed solution are mutually aggregated into wet particles of hundreds of nanometers, and then the wet particles are aggregated to form a wet particle with a three-dimensional network structure and suspended in the dispersion medium. Then, the wet gel with three-dimensional network structure is broken in the large amount of aqueous dispersion solvent, so that the wet gel is broken into particles with the diameter ranging from hundreds of micrometers to tens of millimeters and is dispersed in the aqueous dispersion solvent. The volume ratio of the mixed solution to the dispersion solvent is 1.5 to 1:4. Similarly, the higher the content of the dispersion solvent is, the lower the agglomeration behavior of the subsequently prepared wet glue is; the higher the base content of the dispersion vehicle, the more severe the macrophase separation and the opaque appearance of the wet gum, but the higher its porosity and the lower its density.
Aging step (S4): the formed hydrophobic aerogel wet glue is aged at a specific temperature, so that the structure of the hydrophobic aerogel wet glue is stable. The aging temperature is, for example, 35 ℃ to 80 ℃, and further, for example, 40 ℃ to 50 ℃.
High-temperature pulse water washing step (S5): and (3) washing the aerogel wet glue by using a 50-95 ℃ high-temperature pulse washing device. On one hand, the high-temperature pulse water washing device utilizes 50-95 ℃ high-temperature water to replace organic components or solvents in the wet glue structure, and matches with a driving force generated by combining a temperature gradient and a concentration gradient to wash the organic substances or the solvents in the wet glue structure, and the water temperature needs to be gradually increased. Generally, the higher the water temperature, the faster the rate of displacement. On the other hand, the pulse wave acting force can also accelerate the water molecules to penetrate into the wet glue particles so as to improve the replacement efficiency with organic components or solvents. On the whole, the high-temperature pulse water washing device can obviously improve the replacement water washing effect of organic components and solvents in the aerogel wet glue. In addition, the higher the acting force frequency of the pulse wave or the larger the winnowing distance is, the higher the washing efficiency is, and the temperature effect and the pulse wave effect can be combined to reduce the whole processing time of the aerogel. The solvent replacement washing efficiency of the high-temperature pulse washing step can be improved by about 30-70%, and the aerogel particles can be completely replaced to be clean within only about 10 minutes of the washing time of the aerogel wet glue particles with the particle size of 2 mm.
Thus, porous hydrophobic aerogel particles having a particle size ranging from several hundred nanometers to several tens of millimeters can be prepared. Furthermore, the hydrophobic aerogel particles can be intermixed with the hydrophilic substrate without drying, such as: the application value of the aerogel particles is improved by mixing cement, cement paint or water-based adhesive. In particular, the hydrophobic aerogel particles can be used as a raw material of a low-temperature cold-proof composite material or a low-temperature aerogel heat insulation blanket so as to exert the heat insulation and cold-proof effects of the aerogel.
Drying step (S6): and (3) distilling at high temperature to remove residual solvent or filtering the residual solvent by using a filter, and quickly drying at 90-160 ℃ under normal pressure to obtain the high-density hydrophobic aerogel particles. Further, the aerogel particles can be dried using a 90 to 250 ℃ fluid bed dryer, a constant temperature oven, a drum dryer, a stirring dryer, or a vacuum dryer to accelerate the drying rate. For example, the high temperature distillation temperature is, for example, 90 to 250 ℃.
A composite step (S7): the aerogel particles and the inorganic fibers which are evaporated and dried by the solvent are mixed with each other in a stirrer to form an evenly dispersed inorganic substance mixture, and then the inorganic glue solution is added to enable the aerogel particles, the inorganic fibers and the inorganic glue solution to interact to form the viscous aerogel composite jelly.
Referring to fig. 2 and 3, the appearance of the hydrophobic aerogel particles with different sizes is observed by a general camera, and it is obvious that the particles have different particle sizes.
Please refer to fig. 4 (a) to 4 (C), which are scanning electron micrographs of hundreds of micron hydrophobic aerogel particles taken with different magnifications, which show that the hydrophobic aerogel particles are formed by stacking a large number of aerogel particles with sizes from about tens of nanometers to hundreds of nanometers and generate a large number of pores.
With continued reference to fig. 5, which is a photograph of the prepared water-repellent aerogel cold-proof insulation brick floating on the water surface, it can be seen that about 80% by volume floats on the water surface and is completely water-repellent, confirming excellent water repellency and low density.
Referring to fig. 6, a photograph of the water-repellent aerogel cold-proof insulating brick cut into a volume of 10.5 cm x7.8 cm shows that the weight of the brick is 144.4g. In other words, the density of the prepared water-repellent aerogel cold-proof insulating brick is about 0.168g/cm 3 It shows a light weight property andand (4) heat insulation effect.
Continuing with FIG. 7, a photograph of the interface angle of the water droplets on the surface of the water-repellent aerogel cold-resistant insulation brick shows that the interface angle of the water droplets on the surface of the insulation brick is about 128 degrees, indicating that it has excellent water-repellent effect.
In view of the above description, it is intended to provide a thorough understanding of the invention, its making and using, and its advantages, the present invention is to be considered as limited only by the scope of the appended claims and are intended to cover all changes and modifications that are within the scope of the invention.

Claims (8)

1. A preparation method of a cold-resisting and heat-insulating hydrophobic aerogel composite jelly comprises the following steps:
mixing: mixing one or more of a siloxane compound, an alkylene siloxane compound, and an R-based-silica oligo with a mixed solvent to form a mixed solution;
a hydrolysis step: adding an acid catalyst into the mixed solution to perform hydrolysis reaction;
condensation step: adding an alkali catalyst into the mixed solution to perform a condensation reaction, wherein a dispersion solvent is added in the condensation reaction process, and the mixed solution is stirred at a high speed to form aerogel wet glue which has a uniform structure, has a particle size ranging from hundreds of nanometers to hundreds of micrometers and is dispersed in the dispersion solvent; or adding a dispersion solvent in the condensation reaction process to enable the mixed solution to form aerogel wet glue with a uniform structure, and crushing the aerogel wet glue in an extra same dispersion solvent environment to enable the aerogel wet glue to be crushed into particles with the diameter ranging from hundreds of micrometers to tens of millimeters and to be dispersed in the dispersion solvent;
and (3) aging: aging the aerogel wet glue structure at a specific temperature to stabilize the aerogel wet glue structure;
high-temperature pulse water washing: washing the aerogel wet glue by using high-temperature pulse water at 50-95 ℃ until the aerogel wet glue is milky;
and (3) drying: removing the solvent by high-temperature distillation or filtering the solvent by a filter, and then drying the aerogel wet gel at high temperature to obtain hydrophobic aerogel particles with high porosity and high specific surface area; and
compounding: mixing the hydrophobic aerogel particles and inorganic fibers with each other in a stirrer to form a uniformly dispersed inorganic mixture, and then adding an inorganic glue solution to enable the aerogel particles, the inorganic fibers and the inorganic glue solution to interact to form a viscous aerogel composite jelly;
wherein: the siloxane compound is tetramethoxysilane or tetraethoxysilane; the alkenyl siloxane compound is methyl trimethoxy silane or methyl triethoxy silane; the R group-silica gel micromolecule is Polydimethylsiloxane (PDMS) or silica gel precursor DMDMDMDMS, the R group is a functional group connected to the tail end of a silica gel molecular chain and comprises-COOH or-NH 2 or-NH 2 or-OH or-COH or-N = C = O or-N-CO-N-, and the number of carbons is from C1 to C6.
2. The method of preparing a cold-resistant, thermally-insulating hydrophobic aerogel composite gel according to claim 1, wherein: the mixed solvent comprises one or more selected from the group consisting of: water, ethanol, toluene, normal hexane, cyclohexane, polyvinyl alcohol and hexadecyl trimethyl ammonium chloride.
3. The method of preparing a cold-resistant, thermally-insulating hydrophobic aerogel composite gel according to claim 1, wherein: the mixed solvent comprises a first component and a second component, the first component comprises one or more substances selected from the group consisting of: water, alcohols, aromatics, and alkanes, the second component being a surfactant comprising one or more selected from the group consisting of: cationic surfactants, anionic surfactants, zwitterionic surfactants, and nonionic surfactants.
4. The method of preparing a cold-resistant, thermally-insulating hydrophobic aerogel composite gel according to claim 1, wherein: the dispersion solvent used in the condensation step comprises one or more of water, alcohols, aromatics and alkanes.
5. The method for preparing a cold-protecting, heat-insulating hydrophobic aerogel composite gel according to claim 1, wherein: the high-temperature distillation elimination in the drying step is rapid drying at 90-160 ℃ and normal pressure, and the high-temperature drying is carried out at 90-250 ℃ by using a fluidized bed dryer, a constant-temperature oven, a drum dryer, a stirring dryer, a spray dryer or a vacuum dryer.
6. The method of preparing a cold-resistant, thermally-insulating hydrophobic aerogel composite gel according to claim 1, wherein: the compounding step is replaced by mutually mixing the hydrophobic aerogel particles directly with inorganic fibers under the stirring force of a stirrer to form an evenly-dispersed inorganic mixture, adding an inorganic glue solution into the inorganic mixture to enable the aerogel particles, the inorganic fibers and the inorganic glue solution to interact to form a sticky aerogel composite jelly, and then adding one or more of water, a sticky agent, a dispersing agent and aerogel powder to adjust the viscosity of the aerogel composite jelly.
7. The method of preparing a cold-resistant, thermally-insulating hydrophobic aerogel composite gel according to claim 6, wherein: the inorganic glue solution is one or more selected from the group consisting of: the phosphate is zirconium phosphate or copper phosphate-oxide, the silicate is aluminum silicate or water glass, and the metal oxide is an oxide of copper, aluminum, zirconium, yttrium or lanthanide.
8. The method of preparing a cold-resistant, thermally-insulating hydrophobic aerogel composite gel according to claim 1, wherein: the inorganic fibers are one or more selected from the group consisting of: ceramic fibers, glass fibers, carbon fibers, oxidized fibers, rock wool fibers, and metal oxide fibers.
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