CN113004776A - Water-based self-repairing coating and application thereof - Google Patents
Water-based self-repairing coating and application thereof Download PDFInfo
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- C09D7/20—Diluents or solvents
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The invention discloses a water-based self-repairing coating and application thereof, and relates to the technical field of coatings. The water-based self-repairing coating comprises a component A, wherein the component A is a mixture of a curing agent and a two-dimensional material and comprises the following components in parts by weight: MXene-Ti2C1-10 parts and water-based isocyanate curing agent 80-100 parts; the aqueous isocyanate curing agent is at least one of Bayer 3100, Tosoh MR200 and Jinhuasheng J3100. The invention provides a water-based polyurea self-repairing coating containing a water-based self-repairing coating, which can respond to visible light and infrared lightSelf-repairing, controllable and quick, and can quickly repair scratches under low laser intensity density.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a water-based self-repairing coating and application thereof.
Background
The polyurea coating is a solvent-free and pollution-free high-performance environment-friendly material, is a novel material developed in recent years after environment-friendly coatings such as high-homogeneity coatings, water-based coatings, photocureable coatings, powder coatings and the like, and is widely applied to the field of material protection such as corrosion prevention, water prevention, wear resistance, damping, protection, earthquake resistance and the like. The first generation of polyurea coating is aromatic polyurea, but the aromatic polyurea is easy to oxidize under ultraviolet irradiation to generate a colored quinoid structure, and the problems of easy yellowing and chalking and the like exist when the coating is used outdoors; the second-generation polyurea is aliphatic polyurea, but in the construction process, the gel time of the aliphatic polyurea is only 3-5S, and the problem of excessively high reaction speed exists, so professional construction equipment is required to be adopted. The above problems limit the application of conventional polyurea coatings. Following the traditional aromatic and aliphatic polyureas, a third generation of a novel polyurea, polyaspartic ester (PAE) polyurea, has emerged. Compared with the traditional polyurea, the PAE polyurea has the advantages of no need of special construction equipment, adjustable curing time, sufficient wetting to a base material, good apparent state of a coating, good color retention, good ultraviolet light resistance and the like.
However, the prior polyaspartic acid ester polyurea is mostly oily, has higher viscosity and is not beneficial to construction; and polyurea coating in the use and transportation process, can be difficult to avoid because the collision with scrape produce crackle and mar, if can not in time restore the crackle and the mar that produce on the coating, the mechanical properties of polymer coating can necessarily descend to shorten the life of material, more importantly, damaged material has huge potential safety hazard. To solve this problem, it is one of the most effective ways to make the coating self-healing.
The self-repairing mechanism mainly comprises: thermoreversible repair, photoreversible repair, and microencapsulated repair. The microcapsule repairing method has complex preparation process and higher cost, has larger limitation on the application of the coating, and can not realize multiple times of repairing; the thermoreversible repair method requires a specific repair environment or condition; the light trigger self-repairing has the characteristic of controllability and rapidness, so that the light trigger self-repairing has great potential in the field of self-repairing. The most effective method for preparing the photo-touch self-repairing coating is to introduce photo-thermal fillers into the system.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide the water-based self-repairing coating which does not contain any organic solvent and volatile organic compounds.
To achieve the above objectThe technical scheme adopted by the invention is as follows: the water-based self-repairing coating comprises a component A, wherein the component A is a mixture of a curing agent and a two-dimensional material and comprises the following components in parts by weight: MXene-Ti2C1-10 parts and water-based isocyanate curing agent 80-100 parts; the aqueous isocyanate curing agent is at least one of Bayer 3100, Tosoh MR200 and Jinhuasheng J3100. The water-based isocyanate curing agent adopted by the application is HDI polyether modified tripolymer, is a hydrophilic curing agent, can have good compatibility with water-based polyaspartic acid ester resin and water-based auxiliary agent, and a paint film obtained by reaction has the advantages of ageing resistance, salt mist resistance, chemical reagent resistance and good mechanical property.
The invention creatively converts MXene-Ti2Adding C into the component A of the water-based self-repairing coating to obtain MXene-Ti2C is a novel transition metal carbon (nitride) two-dimensional crystal, and has a lamellar structure similar to graphene. The material can be obtained by dissociating the MAX phase of the layered ceramic material by hydrofluoric acid, and has excellent mechanical, electronic and magnetic properties. The latest research finds that MXene-Ti2The C has good photo-generated heat effect under the irradiation of visible-near infrared light, and the photo-thermal conversion rate is as high as 85%. And, unlike graphene, MXene-Ti2Since C has hydrophilic property due to the presence of functional groups such as-OH and-COOH on the surface, MXene-Ti2The C can be widely applied to water-based paint as photo-thermal filler. Furthermore, MXene-Ti is used as a main component2The C has unique two-dimensional sheet structure and excellent mechanical property, so that the C can be uniformly dispersed in a matrix to improve the mechanical properties of a paint film, such as tensile strength, hardness and the like.
MXene-Ti2C and an aqueous isocyanate curing agent, Ti2C can be uniformly dispersed in the curing agent, does not aggregate and has moderate viscosity; the water-based isocyanate curing agent can be better dispersed in water through hydrophilic modification, a hydrophilic solvent is generally used as a medium and is used as a component A of the water-based self-repairing coating, and the prepared water-based self-repairing coating which is prepared by using water as the solvent, does not contain any organic solvent, does not contain volatile organic matters and is very environment-friendly is prepared.
Preferably, the component A comprises the following components in parts by weight: MXene-Ti21-5 parts of C and 80-90 parts of water-based isocyanate curing agent. The inventor researches MXene-Ti through a large number of creative tests2The optimal dosage range of C and Bayer 3100 is matched, the hydrophilicity of the waterborne self-repairing coating formed in the interval is better, and the mechanical property of the prepared coating is better.
Further preferably, the component A comprises the following components in parts by weight: MXene-Ti2C3 parts and 85 parts of a water-based isocyanate curing agent. The inventor researches MXene-Ti through a large number of creative tests2C and the water-based isocyanate curing agent are used in an optimal amount in a matching way, so that the formed water-based self-repairing coating has the best hydrophilicity, and the prepared coating has the best mechanical property.
Preferably, the water-based self-repairing coating further comprises a component B, wherein the component B is a mixture of resin and other auxiliaries, and comprises the following components in parts by weight: 60-80 parts of water-based polyaspartic acid ester resin and MXene-Ti21-5 parts of C, 15-20 parts of water, 20-30 parts of pigment and filler and 1-5 parts of auxiliary agent.
Adding hydrophilic photo-thermal filler MXene-Ti into component B of water-based self-repairing coating2C，MXene-Ti2The addition of C increases the tensile strength and hardness of the coating. MXene-Ti2C has very high photothermal effect, high heat-conducting property, special structural performance and good compatibility with aqueous resin, so that the coating has very high photothermal conversion effect, the coating can respond to near infrared-visible light, the surface temperature of the coating is obviously increased after the coating is irradiated by light radiation, the mechanical damage of the coating can be quickly and automatically repaired by the rapid increase of the surface temperature of the coating, the loss in processing and use is avoided, and the long-term protection of the base material is realized.
Preferably, the aqueous polyaspartic ester resin is LA-50; the pigment filler is a mixture of titanium dioxide, bentonite and silicon dioxide; the auxiliary agent comprises a dispersing agent, a flatting agent, an antifoaming agent and a thixotropic agent, wherein the mass ratio of the dispersing agent to the flatting agent to the antifoaming agent to the thixotropic agent is as follows: dispersing agent: leveling agent: defoaming agent: the thixotropic agent is 1-2:0.5-1:1-2: 1-2. Further preferably, the mass ratio of titanium dioxide, bentonite and silicon dioxide in the pigment filler is as follows: titanium dioxide: bentonite: silica 1:1: 1-2; the mass ratio of the dispersing agent to the flatting agent to the defoaming agent to the thixotropic agent in the auxiliary agent is as follows: dispersing agent: leveling agent: defoaming agent: the thixotropic agent is 1:0.5:1: 1. Wherein the dispersant is at least one of PE100, KYC-9366 and AKN-2276; the leveling agent is at least one of BYK346, KMT01972 and KYC-616; the defoaming agent is at least one of BYK-028, GP330 and QX-10S; the thixotropic agent is at least one of LV, KMT-40 and AKN-7020; are all common commercial products.
Titanium dioxide is a white pigment that is considered to be the best performing in the world today, with no toxicity, optimal opacity, optimal whiteness and brightness. The titanium dioxide has strong adhesive force, is not easy to chemically change, is always snow white and plays a role in covering power; the bentonite can form gel in various organic solvents, oils and liquid resins, has good thickening property, thixotropy, suspension stability, high-temperature stability, lubricity, film-forming property, water resistance and chemical stability, and has important application value in the paint industry; the silicon dioxide has chemical stability and lubricity and does not react with acid and alkali, and the salt spray resistance, the chemical reagent resistance, the flexibility and the hardness of the coating film can be obviously improved by adding the silicon dioxide.
In addition, the invention also provides MXene-Ti2The preparation method of C comprises the following steps:
(1) adding MAX phase material Ti2Adding AlC into HF, stirring and etching to obtain a mixture, filtering the mixture to obtain a solid, washing the solid with water until the pH value of a washing liquid is 5.5-6.5, and drying to obtain a multilayer MXene-Ti2C；
(2) The multilayer MXene-Ti prepared in the step (1) is2C and DMSO are mixed and stirred for 12-24h for intercalation, solid is obtained after ultrasonic filtration, and MXene-Ti is obtained after drying2C。
Preferably, the weight ratio of the A component to the B component is: the component A comprises: the component B is 1-2: 1-2. The inventor of the application finds that the A, B component in the proportion range has moderate mixing viscosity and moderate reaction time through a large amount of creative experimental research, and the obtained paint film is uniform and smooth and has excellent performance.
Further preferably, the weight ratio of the A component to the B component is: the component A comprises: and the component B is 1: 1. Through a large amount of creative experimental researches, the inventor of the application finds that when the weight ratio of the component A to the component B is 1:1, the obtained paint film has the best performance.
Meanwhile, the invention also provides a water-based polyurea self-repairing coating containing the water-based self-repairing coating.
In addition, the invention also provides a preparation method of the water-based polyurea self-repairing coating, which comprises the following steps:
(1) uniformly mixing the component A, and adding the component A into the uniformly mixed component B to obtain the water-based self-repairing coating;
(2) and (2) uniformly mixing the water-based self-repairing coating obtained in the step (1), and spraying, manually brushing or rolling the coating on metal within less than 15min to obtain the water-based polyurea self-repairing coating.
Preferably, the metal is at least one of copper, iron, aluminum and stainless steel.
Compared with the prior art, the invention has the beneficial effects that: (1) the coating disclosed by the invention can be self-repaired by responding to visible light and infrared light, has the characteristics of controllability and rapidness, and can be used for rapidly repairing scratches under the condition of low laser intensity density. (2) The invention adopts water as a solvent, does not contain any organic solvent, does not contain volatile organic compounds, and is very environment-friendly. (3) The polyurea coating prepared by the invention has full color, the hardness reaches 3H, the tensile strength reaches 26.4Mpa, the elongation at break reaches 300%, the tearing strength reaches 57.2Mpa, and meanwhile, the paint film has excellent waterproof, anticorrosion and weather-resistant properties. (4) The method has the advantages of simple process, energy conservation and environmental protection, and is suitable for large-scale production.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Examples 1-5 are provided herein, with specific examples 1-5 having components and parts by weight selected as shown in tables 1 and 2:
TABLE 1 selection of parts by weight of examples 1-5
TABLE 2 selection of Components for examples 1-5
The preparation method of the water-based polyurea self-repairing coating disclosed by the embodiment comprises the following steps after the components are weighed according to the following table 1 and table 2:
(1) uniformly mixing the component A, and adding the component A into the uniformly mixed component B to obtain the water-based self-repairing coating;
(2) and (2) spraying, manually brushing or rolling the water-based self-repairing coating obtained in the step (1) on metal within less than 15min to obtain the water-based polyurea self-repairing coating.
Wherein MXene-Ti is used in the invention2The preparation method of C comprises the following steps:
(1) 10g of a MAX phase material Ti2Adding AlC into 100ml of 10% HF, stirring for 24h for etching to obtain a mixture, filtering the mixture to obtain a solid, washing the solid with water until the pH value of a water washing solution is 5.5-6.5, and drying to obtain a multilayer MXene-Ti2C；
(2) The multilayer MXene-Ti prepared in the step (1) is2C and DMSO are mixed and stirred for 20 hours for intercalation, and the intercalation is obtained after ultrasonic filtrationA solid, wherein the MXene-Ti is obtained after ultrasonic drying for 2h at 300w2C。
Meanwhile, the application is provided with comparative examples, and the specific comparative examples are as follows:
MXene-Ti was not contained in the A component of comparative example 12C, the rest components, the parts by weight and the preparation method are completely the same as the embodiment 5;
MXene-Ti was not contained in the B component of comparative example 22C, the rest components, the parts by weight and the preparation method are completely the same as the embodiment 5;
the curing agent in the component A of the comparative example 3 is JX615, and the rest components, the parts by weight and the preparation method are completely the same as those in the example 5;
the resin in the component B of the comparative example 4 is waterborne polyurethane PU3946, and the rest components, the parts by weight and the preparation method are completely the same as those in the example 5;
test example 1 test procedure of self-repair test of coating: scratching a scratch with a width of less than 100 μm on the coating layer after complete curing with a sharp blade, respectively using 473nm visible light with a light intensity density of 3.5W cm-2Irradiating; and 785nm near infrared laser with light intensity density of 2.0W cm-2Irradiating;
and (3) test results: the test results are shown in tables 3 and 4
TABLE 3 test results of examples 1 to 5 and comparative examples 1 to 4 irradiated with 473nm visible light
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Self-repairing time (min) | 10 | 12 | 9 | 8 | 5 |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||
| Self-repairing time (min) | 20 | 18 | 15 | / |
TABLE 4 results of 785nm NIR laser irradiation tests on examples 1-5 and comparative examples 1-4
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Self-repairing time (min) | 9 | 10 | 8 | 6 | 3 |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||
| Self-repairing time (min) | 17 | 15 | 14 | / |
As can be seen from tables 3 and 4, the water-based polyurea self-repairing coating prepared by the embodiment of the application can perform self-repairing on response of visible light and infrared light, and the repairing time is short; the application is rightThe proportion 4 adopts the waterborne polyurethane PU3946, scratches cannot be repaired, the waterborne polyaspartic ester resin selected by the application is obtained through a large number of creative experiments, and the effect of the application cannot be obtained by adopting other components; comparative examples 1 and 2 were each MXene-Ti-free in component A2MXene-Ti is not contained in the C and B components2C, the self-repairing time is obviously prolonged, and the repairing effect is not obvious; the curing agent in the component A of the comparative example 3 is JX615, which is not a water-based isocyanate curing agent, and the repairing time is longer and the effect is not obvious.
Test example 2 Performance test
And (4) testing standard: as shown in table 5:
and (3) testing results: as shown in table 5:
TABLE 5 results of performance test of examples and comparative examples
As can be seen from Table 5, the polyurea coating prepared by the embodiment of the invention has full color, the hardness reaches 3H, the tensile strength reaches 26.4MPa, the elongation at break reaches 300%, the tear strength reaches 57.2MPa, and meanwhile, the paint film has excellent waterproof, anticorrosion and weather-resistant properties, wherein the effect of the embodiment 5 is the best. The comparative example does not adopt the components selected by the invention, and the effect of the invention can not be achieved, and the difference is huge.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The water-based self-repairing coating is characterized by comprising a component A, wherein the component A is a mixture of a curing agent and a two-dimensional material and comprises the following components in parts by weight: MXene-Ti2C1-10 parts and water-based isocyanate80-100 parts of a curing agent; wherein the aqueous isocyanate curing agent is at least one of Bayer 3100, Toso MR200 and Jinhuasheng J3100.
2. The aqueous self-repairing coating of claim 1, wherein the A component comprises the following components in parts by weight: MXene-Ti21-5 parts of C and 80-90 parts of water-based isocyanate curing agent.
3. The aqueous self-repairing coating of claim 2, wherein the A component comprises the following components in parts by weight: MXene-Ti2C3 parts and 85 parts of a water-based isocyanate curing agent.
4. The aqueous self-repairing coating of claim 1, further comprising a component B, wherein the component B is a mixture of resin and other auxiliaries, and comprises the following components in parts by weight: 60-80 parts of water-based polyaspartic acid ester resin and MXene-Ti21-5 parts of C, 15-20 parts of water, 20-30 parts of pigment and filler and 1-5 parts of auxiliary agent.
5. The aqueous self-healing coating of claim 4, wherein the aqueous polyaspartate resin is LA-50; the pigment filler is a mixture of titanium dioxide, bentonite and silicon dioxide; the auxiliary agent comprises a dispersing agent, a flatting agent, an antifoaming agent and a thixotropic agent, wherein the mass ratio of the dispersing agent to the flatting agent to the antifoaming agent to the thixotropic agent is as follows: dispersing agent: leveling agent: defoaming agent: the thixotropic agent is 1-2:0.5-1:1-2: 1-2.
6. The aqueous self-repairing coating of claim 5, wherein the mass ratio of titanium dioxide, bentonite and silicon dioxide in the pigment filler is as follows: titanium dioxide: bentonite: silica 1:1: 1-2; the mass ratio of the dispersing agent to the flatting agent to the defoaming agent to the thixotropic agent in the auxiliary agent is as follows: dispersing agent: leveling agent: defoaming agent: the thixotropic agent is 1:0.5:1: 1.
7. As in claimThe aqueous self-repairing coating of any one of claims 1 to 6, wherein MXene-Ti is present2The preparation method of C comprises the following steps:
(1) adding MAX phase material Ti2Adding AlC into HF, stirring and etching to obtain a mixture, filtering the mixture to obtain a solid, washing the solid with water until the pH value of a washing liquid is 5.5-6.5, and drying to obtain a multilayer MXene-Ti2C；
(2) The multilayer MXene-Ti prepared in the step (1) is2C and DMSO are mixed and stirred for 12-24h for intercalation, solid is obtained after ultrasonic filtration, and MXene-Ti is obtained after drying2C。
8. The aqueous self-healing coating of any one of claims 4 to 6, wherein the weight ratio of the A component to the B component is: the component A comprises: the component B is 1-2: 1-2.
9. A water-based polyurea self-healing coating, comprising the water-based self-healing coating of claim 8 or 9.
10. The method for preparing the aqueous polyurea self-healing coating of claim 9, comprising the steps of:
(1) uniformly mixing the component A, and adding the component A into the uniformly mixed component B to obtain the water-based self-repairing coating;
(2) and (2) uniformly mixing the water-based self-repairing coating obtained in the step (1), and spraying, manually brushing or rolling the coating on metal within less than 15min to obtain the water-based polyurea self-repairing coating.
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Cited By (5)
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| CN114539762A (en) * | 2022-02-21 | 2022-05-27 | 北京理工大学 | MXene/polyurethane composite material with friction resistance and preparation method thereof |
| CN115304992A (en) * | 2022-08-17 | 2022-11-08 | 南京林业大学 | Water-assisted room temperature self-repairing polyurethane insulating coating and preparation method thereof |
| CN115746233A (en) * | 2022-11-10 | 2023-03-07 | 沈阳航空航天大学 | Modified graphene-enhanced repairable multifunctional asparagus polyurea elastomer composite material and preparation method thereof |
| CN116218344A (en) * | 2023-03-31 | 2023-06-06 | 中国科学院长春应用化学研究所 | A kind of water-based air-filled structural material surface repair agent and its preparation method and application |
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Application publication date: 20210622 |