CN113292894A - Aerogel coating and aerogel coating obtained from aerogel coating - Google Patents
Aerogel coating and aerogel coating obtained from aerogel coating Download PDFInfo
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- CN113292894A CN113292894A CN202110525845.2A CN202110525845A CN113292894A CN 113292894 A CN113292894 A CN 113292894A CN 202110525845 A CN202110525845 A CN 202110525845A CN 113292894 A CN113292894 A CN 113292894A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
- Y02B80/10—Insulation, e.g. vacuum or aerogel insulation
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Abstract
Disclosed is an aerogel coating, comprising: film forming emulsion; SiC-SiO2Compounding aerogel; a dispersant; a wetting agent; defoaming agents; rutile titanium dioxide nanoparticles; hollow glass beads; a thickener; a film-forming aid; ammonia water; the balance of deionized water. Aerogel coatings derived from the aerogel coatings are also disclosed. The aerogel improves surface energy and a connection area of secondary particles, thereby improving mechanical properties and heat insulation properties.
Description
Technical Field
The invention belongs to the technical field of aerogel nano materials; relates to an aerogel coating and an aerogel coating obtained from the aerogel coating.
Background
In recent years, the heat insulation coating is gradually attracted by people, is a functional water-based coating, and can play roles in reflecting sunlight energy, delaying heat transfer and actively cooling radiant heat mainly by adding a filler with functions of reflecting sunlight, blocking heat transfer and radiating energy into film-forming resin, so that industrial and building materials can obtain heat insulation and heat preservation effects. Compared with the traditional heat insulation material, the heat insulation coating has better construction convenience and is not easy to fall off. Therefore, the heat insulation coating is an ideal substitute of the traditional heat insulation material and has good application and research prospects.
SiO2The aerogel is a porous heat-insulating material, has high porosity (more than 99.8 percent) and pore diameter in a nanoscale range,the thermal conductivity is lower than that of room temperature air (0.013W/(mK)), so that SiO2Aerogel is also called super heat insulation material, and is widely applied in the fields of heat preservation and heat insulation of industrial and building materials.
Chinese patent application CN107858050A discloses a SiO2The aerogel heat insulation coating comprises the following components in parts by weight: 50-100 parts of base paint and 5-20 parts of SiO2Aerogel, 2-10 parts of hollow glass beads with titanium dioxide coatings, 0.05-0.2 part of dimethyl hydroxyl silicone oil, 0.05-0.2 part of hexadecyl trimethyl ammonium bromide, 10-25 parts of curing agents and 2-10 parts of auxiliaries; the auxiliary agent comprises a dispersing agent, a wetting agent, a defoaming agent and a flatting agent. The SiO2In the aerogel heat-insulating and heat-preserving coating, SiO2The aerogel is matched with the hollow glass beads with the coating, and the heat preservation and insulation effects are improved in a synergistic mode.
However, in this patent application, SiO2The aerogel is not subjected to any surface modification, belongs to a hydrophobic substance and has poor compatibility with an acrylic emulsion used as a matrix paint; at the same time, SiO2The aerogel has higher surface energy, is easy to agglomerate, and has smaller connecting area of secondary particles, thus leading to poor heat insulation effect and poor mechanical property of the coating.
In view of the above-mentioned drawbacks of the prior art, there is a strong need to find an aerogel coating and an aerogel coating obtained from the aerogel coating.
Disclosure of Invention
The invention aims to provide an aerogel coating and an aerogel coating obtained from the aerogel coating. The aerogel coating not only has better heat insulation effect; meanwhile, the mechanical property is better.
In order to achieve the above object, the present invention provides an aerogel coating, which comprises the following components:
30-50 wt% of film-forming emulsion;
SiC-SiO210-20 wt% of composite aerogel;
1-3 wt% of a dispersant;
0.1-0.3 wt% of wetting agent;
0.1-0.5 wt% of defoaming agent;
2-6 wt% of rutile type titanium dioxide nano particles;
2-6 wt% of hollow glass beads;
1-3 wt% of a thickener;
0.5-2 wt% of film-forming assistant;
0.2 to 0.8 weight percent of ammonia water;
the balance of deionized water;
it is characterized in that the preparation method is characterized in that,
the SiC-SiO2The composite aerogel is selected from polyacrylic acid modified SiC-SiO2And (3) compounding the aerogel.
The aerogel coating of the invention, wherein the film-forming emulsion is selected from flexible acrylic emulsions, and the solid content is 50-60%.
The aerogel coating according to the present invention, wherein the dispersant is selected from ammonium polyacrylate salts.
The aerogel coating according to the present invention, wherein the wetting agent is selected from a polyether modified polydimethylsiloxane solution.
The aerogel coating according to the present invention, wherein the defoamer is selected from silicone defoamers.
The aerogel coating according to the invention, wherein the thickener is selected from anionic thickeners.
The aerogel coating according to the present invention, wherein the adjuvant is selected from alcohol ester-12.
The aerogel coating of the invention, wherein the SiC-SiO2The composite aerogel is obtained by gelatinizing a mixed solution of SiC nano-particles, silica sol, ethanol, water and dimethylformamide and then drying the gelled mixed solution at normal pressure.
Advantageously, the SiC nanoparticles have an average particle size of 20-60 nm.
Advantageously, the silica sol has an average particle size of from 10 to 20nm and a solids content of from 20 to 40%.
Advantageously, the weight to volume ratio of SiC nanoparticles to silica sol is (2-4) g: 100 mL.
Advantageously, the volume ratio of silica sol, ethanol and water is (6-10): (12-20): 1.
advantageously, dimethylformamide is added in an amount of 0.5 to 1.5% by volume of the mixture.
Advantageously, the SiC-SiO2The preparation method of the composite aerogel comprises the following steps:
dispersing SiC nano particles in ethanol to obtain SiC dispersion liquid;
adding silica sol, ethanol, water and dimethylformamide into the SiC dispersion liquid to obtain a mixed liquid;
gelatinizing the mixed solution;
optionally, aging, solvent exchange;
drying under normal pressure.
The aerogel coating according to the present invention, wherein the polyacrylic acid-modified SiC — SiO2The preparation method of the composite aerogel comprises the following steps:
SiC-SiO2KH-570 modification is carried out on the composite aerogel;
modified SiC-SiO2Reacting the composite aerogel with an acrylic monomer; advantageously, the weight to volume ratio of the two is 1 g: (0.1-0.3) mL.
In another aspect, the present invention provides an aerogel coating, wherein the aerogel coating is obtained by coating the aerogel coating according to the present invention on a substrate and curing.
The invention has the beneficial effects that: compared with the prior art, the aerogel coating has better heat insulation effect; meanwhile, the mechanical property is better.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the scope of the invention.
In the specific embodiment of the invention, the SiC nano-particles are purchased from Beijing Deke island gold science and technology Co., Ltd, and the product model is DK-SiC-001; the average particle diameter is 40nm, and the bulk density is 0.11g/cm3The specific surface area is 39.8m2/g。
The silica sol is purchased from Beijing Deke island gold science and technology Limited, and has a product model of JL-SiO2-Z15, an average particle size of 15nm and a solid content of 30 percent.
KH-570 was obtained from Shanghai permanent research chemical technology Co.
The flexible acrylic emulsion (film-forming emulsion) is purchased from Shanghai Baolijia chemical company Limited, and has the product model of BLJ-963M and the solid content of 54 percent.
Ammonium polyacrylate salt (dispersant OROTAN 1124) was purchased from Rohm and Haas, China, USA, and has a solid content of 50%.
The polyether modified polydimethylsiloxane solution (wetting agent BYK-306) was purchased from BYK, Germany.
Silicone antifoam (ADEKA NATE B-199) was purchased from Shanghai Edisco Fine chemical Co., Ltd at a viscosity of 2500 cP.
The rutile type titanium dioxide nanoparticles are purchased from Beijing Deke island gold science and technology Limited company, the product model is DK405-3, the average particle size is 200nm, and the specific surface area is 15m2/g。
The hollow glass beads are purchased from Shanghai Hui Jing sub-nanometer new material Co Ltd, the product model is S-38, the 50 percent particle size is below 40nm, and the volume density is 0.38g/cm3。
Anionic thickener (TT-935) was purchased from Rohm and Haas China, USA, and has a solid content of 30%.
Coalescing agent alcohol ester-12 was purchased from Istmann chemical Co., Ltd.
Modification of SiC nanoparticles
50mL of a 2% by volume KH-570 ethanol solution was prepared, and the pH was adjusted to 4.0 using acetic acid. 10g of SiC nanoparticles were added to the above KH-570 ethanol solution, and modification reaction was carried out at 55 ℃. After the reaction was completed, the reaction mixture was centrifuged at 12000rpm for 10min to obtain a solid precipitate. Washed 3 times with absolute ethanol and dried at 80 ℃ to obtain modified SiC nanoparticles (a 1).
SiC-SiO2Preparation of composite aerogels
1.2g of modified SiC nanoparticles are added into 80mL of absolute ethanol, and the mixture is subjected to ultrasonic treatment to be uniformly dispersed, so that SiC ethanol dispersion liquid is obtained. 40mL of silica sol (with a solid content of 30%) and 5mL of deionized water were added to the SiC ethanol dispersion, and then 1mL of dimethylformamide DMF was added, and the mixture was dispersed uniformly by sonication. At room temperatureStanding to obtain SiC-SiO2Compounding the wet gel. Aging at room temperature for 24h after wet gel formation; and then respectively soaking the mixture for 24 hours by using ethanol water solution with the volume concentration of 50% and absolute ethanol, and replacing the corresponding solution once in 8 hours. Finally, drying for 48h at 60 ℃ to obtain SiC-SiO2Composite aerogel (a 2).
SiC-SiO2Modification of composite aerogels
5g of SiC-SiO2And (3) putting the composite aerogel into 60mL of ethanol, adding 0.5mL of 25% ammonia water solution, and performing ultrasonic treatment to uniformly disperse the composite aerogel. Adding 1g of KH-570, performing ultrasonic treatment to uniformly disperse the KH-570, and reacting for 36 hours at 70 ℃ under a closed condition; then the opening is heated for 4 h. After the reaction was completed, the reaction mixture was centrifuged at 12000rpm for 10min to obtain a solid precipitate. Washing with anhydrous ethanol for 3 times, and drying at 80 deg.C to obtain KH-570 modified SiC-SiO2Composite aerogel (a 3). Then 1g of KH-570 modified SiC-SiO2The composite aerogel is dispersed in 9mL of absolute ethyl alcohol, 10mL of 2% acrylic monomer ethanol solution with volume concentration and 10mL of 0.015g of potassium persulfate aqueous solution are sequentially added in a nitrogen atmosphere, and the mixture is reacted for 12 hours at the temperature of 80 ℃. After the reaction was completed, the reaction mixture was centrifuged at 12000rpm for 10min to obtain a solid precipitate. Washing with anhydrous ethanol for 3 times, and drying at 80 deg.C to obtain polyacrylic acid modified SiC-SiO2Composite aerogel (a 4).
Preparation of aerogel thermal insulation coating
The aerogel thermal insulation coating comprises the following formula: BLJ-963M 40 wt%; polyacrylic acid modified SiC-SiO215 wt% of composite aerogel (a 4); OROTAN 11242 wt%; BYK-3060.2 wt%; 2371ADEKA NATE B-1990.3 wt%; DK 405-34 wt%; s-384%; TT-9352 wt%; alcohol ester-121 wt%; 0.5 wt% of ammonia water; the balance of deionized water.
Adding OROTAN 1124, BYK-306 and B-199 in the formula amount of 1/2 into deionized water, and stirring to mix them uniformly; then adding formula amount of polyacrylic acid modified SiC-SiO2Homogenizing the composite aerogel (A4) at 8000rpm for 10 min; adding DK405-3 with the formula amount, and stirring to uniformly mix; adding BLJ-963M, alcohol ester-12 and S-38 in the formula ratio, and stirringStirring to mix well; then adding ammonia water and 1/2 formula amount of B-199, stirring to mix them uniformly; and finally, adding TT-935, and stirring to uniformly mix the mixture to obtain the aerogel thermal insulation coating.
Thermal insulation test
The heat insulation test is carried out according to the national standard GB/T25261-2018. The heat insulation temperature difference testing device comprises a heating device (250W infrared lamp), a temperature testing device (a Pt resistance probe and an automatic temperature display instrument) and a heat insulation box (which is formed by six polyethylene foam plates of 36cmX36cmX3cm, the heat conductivity coefficient of the polyethylene foam plates is 0.023W/mK; a square hole of 15cmX7.5cmX3cm is cut in the polyethylene foam plate at the top for placing a test sample plate or a blank sample plate); the heating device is positioned at a position 30cm above the center of the test sample plate; the Pt resistance probe was in contact with the bottom of the test panel. The test panels were coated with 1mm thick aerogel thermal barrier coating. The temperature of the blank and test panels after 60min heating were recorded separately. The difference value is used as the insulation temperature difference. The thermal insulation temperature difference of the aerogel thermal insulation coating is 18.6 ℃.
Adhesion test
The adhesion test was performed according to the cross-hatch method of the national standard GB/T1720-.
The adhesive force of the aerogel thermal insulation coating is grade 1.
Comparative test
With SiC-SiO2Composite aerogel (A2) and KH-570 modified SiC-SiO2Replacement of polyacrylic acid modified SiC-SiO by composite aerogel (A3)2And (3) preparing the aerogel thermal insulation coating according to the same method, and respectively carrying out a thermal insulation test and an adhesion test on the composite aerogel (A4). The results show that the adiabatic temperature differences of (A2) and (A3) are 12.7 ℃ and 11.4 ℃, respectively; the adhesive force is 2 grades.
The SiC-SiO was carried out sequentially by replacing the modified SiC nanoparticles (A1) with the unmodified SiC nanoparticles (A1')2Composite aerogel (A2'), KH-570 modified SiC-SiO2Composite aerogel (A3') and polyacrylic acid modified SiC-SiO2Composite aerogel (a4 '), prepared by replacing (a4) with (a 4') according to the same method, and subjected to heat insulation test and adhesion test, respectively. The results show that the method has the advantages of high yield,(A4') each had an adiabatic temperature difference of 16.9 ℃; the adhesive force is 1 grade.
Without wishing to be bound by any theory, the use of the particular aerogels of the invention improves SiO2The surface energy of the aerogel and the connection area of the secondary particles, thereby improving the mechanical properties and the heat insulation properties.
It should be understood that the detailed description of the invention is merely illustrative of the spirit and principles of the invention and is not intended to limit the scope of the invention. Furthermore, it should be understood that various changes, substitutions, deletions, modifications or adjustments may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are also within the scope of the invention as defined in the appended claims.
Claims (10)
1. An aerogel coating, the formulation of the aerogel coating being as follows:
30-50 wt% of film-forming emulsion;
SiC-SiO210-20 wt% of composite aerogel;
1-3 wt% of a dispersant;
0.1-0.3 wt% of wetting agent;
0.1-0.5 wt% of defoaming agent;
2-6 wt% of rutile type titanium dioxide nano particles;
2-6 wt% of hollow glass beads;
1-3 wt% of a thickener;
0.5-2 wt% of film-forming assistant;
0.2 to 0.8 weight percent of ammonia water;
the balance of deionized water;
it is characterized in that the preparation method is characterized in that,
the SiC-SiO2The composite aerogel is selected from polyacrylic acid modified SiC-SiO2And (3) compounding the aerogel.
2. The aerogel coating of claim 1, wherein the film-forming emulsion is selected from flexible acrylic emulsions having a solids content of 50-60%.
3. The aerogel coating of claim 1, wherein the dispersant is selected from ammonium polyacrylate salts.
4. The aerogel coating of claim 1, wherein the wetting agent is selected from a polyether modified polydimethylsiloxane solution.
5. The aerogel coating of claim 1, wherein the defoamer is selected from silicone defoamers.
6. The aerogel coating of claim 1, wherein the thickener is selected from anionic thickeners.
7. The aerogel coating of claim 1, wherein the adjuvant is selected from alcohol ester-12.
8. The aerogel coating of claim 1, wherein SiC-SiO2The composite aerogel is obtained by gelatinizing a mixed solution of SiC nano-particles, silica sol, ethanol, water and dimethylformamide and then drying the gelled mixed solution at normal pressure.
9. The aerogel coating of claim 1, wherein the polyacrylic acid-modified SiC-SiO2The preparation method of the composite aerogel comprises the following steps:
SiC-SiO2KH-570 modification is carried out on the composite aerogel;
modified SiC-SiO2Reacting the composite aerogel with an acrylic monomer; advantageously, the weight to volume ratio of the two is 1 g: (0.1-0.3) mL.
10. An aerogel coating obtained by curing an aerogel coating according to any of claims 1 to 9 applied on a substrate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104692757A (en) * | 2015-02-15 | 2015-06-10 | 金成� | Short SiC fiber/SiO2 aerogel composite material and preparation method thereof |
| CN111675941A (en) * | 2020-07-24 | 2020-09-18 | 常州广树化工科技有限公司 | Preparation method of water-based heat-insulating and cooling coating |
| CN111777952A (en) * | 2020-06-12 | 2020-10-16 | 上海嗣高新材料科技有限公司 | Aerogel and nano hydrotalcite synergistic fireproof sealant and preparation method thereof |
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- 2021-05-14 CN CN202110525845.2A patent/CN113292894B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104692757A (en) * | 2015-02-15 | 2015-06-10 | 金成� | Short SiC fiber/SiO2 aerogel composite material and preparation method thereof |
| CN111777952A (en) * | 2020-06-12 | 2020-10-16 | 上海嗣高新材料科技有限公司 | Aerogel and nano hydrotalcite synergistic fireproof sealant and preparation method thereof |
| CN111675941A (en) * | 2020-07-24 | 2020-09-18 | 常州广树化工科技有限公司 | Preparation method of water-based heat-insulating and cooling coating |
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Address after: 221100 east of Yinshan road and south of Lijiang Road, No.2 Industrial Park, Tongshan District, Xuzhou City, Jiangsu Province, 1st floor, building A9, Safety Technology Industrial Park Patentee after: Anhua New Materials Technology (Jiangsu) Co.,Ltd. Address before: 221100 east of Yinshan road and south of Lijiang Road, No.2 Industrial Park, Tongshan District, Xuzhou City, Jiangsu Province, 1st floor, building A9, Safety Technology Industrial Park Patentee before: ANHUA FIRE-FIGHTING NEW MATERIAL TECHNOLOGY (JIANGSU) Co.,Ltd. |