CN113956790A - Organic silicon coating and preparation method thereof - Google Patents
Organic silicon coating and preparation method 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- 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
- C09D7/63—Additives non-macromolecular organic
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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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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The application relates to an organic silicon coating and a preparation method thereof. The organic silicon coating comprises 25-35 parts by weight of alpha, omega-dihydroxy polysiloxane, 1-3 parts by weight of hydroxy silicone oil, 1-3 parts by weight of n-dodecyl trimethoxy silane, 15-25 parts by weight of ground calcium carbonate, 3-5 parts by weight of nano calcium carbonate, 1-3 parts by weight of fumed silica, 0.1-3 parts by weight of pigment, 30-40 parts by weight of diluent, 0.1-3 parts by weight of molecular sieve, 2-5 parts by weight of cross-linking agent, 0.1-3 parts by weight of catalyst, 0.1-3 parts by weight of vinyl trimethoxy silane, 0.1-3 parts by weight of tackifier and 0.1-3 parts by weight of coupling agent. The organic silicon coating has the advantages of short curing time, less surface drying/actual drying time, strong adhesive force, good storage stability and the like.
Description
Technical Field
The invention relates to the field of organic silicon, and particularly relates to an organic silicon coating and a preparation method thereof.
Background
The room temperature curing organosilicon coating is prepared by taking alpha, omega dihydroxy polydimethylsiloxane with medium and low viscosity as a base adhesive, taking an organic tin chelate as a catalyst, taking methyl tributyrinoxime silane and vinyl tributyrinoxime silane as cross-linking agents, taking propylamino triethoxysilane as a tackifier, adding a filler and a solvent, and preparing. The products thus produced suffer mainly from the following 3 problems: 1. the surface drying time is long, the internal curing speed is slow, and the use of customers is influenced; 2. when the coating is used as a three-proofing paint, the coating has poor adhesion to a contacted base material and is easy to peel off; 3. the storage stability of the product is poor. This is because the room temperature-curable silicone coating is crosslinked and cured immediately upon contact with water, and the curing speed is also related to the migration and penetration of moisture and crosslinking agent in the silicone coating. Therefore, the moisture content of each component must be strictly controlled during the production process and performed in a dry environment to avoid the loss of value of the rubber compound due to curing during production and storage.
Chinese patent CN102559047A discloses that the organosilicon elastic coating adopts trifunctional ketoxime type silane coupling agent as the cross-linking agent of the silicone rubber, organic tin as the catalyst, propylamino triethoxysilane and 3-glycidoxypropyltrimethoxysilane as the adhesion promoter, and solvent oil or petroleum ether as the solvent. In the curing process of the product, a solvent is volatilized, the viscosity is gradually increased to form a coating film, the coating film is coated on a base material, meanwhile, a silane coupling agent in the coating film is rapidly hydrolyzed when contacting with moisture in the air, under the promotion of a catalyst, a condensation reaction is carried out between the crosslinking agent and active terminal hydroxyl of the organic silicon polymer, low molecular substances generated by the reaction are removed, the chain reaction of hydrolysis-condensation-removal of the low molecular substances is gradually carried out, and finally, a crosslinking network of the organic silicon polymer is formed, so that the crosslinking vulcanization of the organic silicon coating is realized. However, the method is lack of a hydroxyl scavenging agent, and can not timely scavenge chemically bound water on the reinforcing filler and free hydroxyl in a system, so that the free hydroxyl in the system can react with the crosslinking agent to cause the crosslinking agent to lose effectiveness in the storage process, and the coating loses the use value.
The Chinese invention patent CN102260456A discloses a method for preparing an organic silicon coating by steps: the hydroxyl-terminated polyorganosiloxane is diluted by the diluent, so that the problem that the prepared organic silicon coating cannot meet the coating requirement easily due to the fact that the crosslinking reaction is generated and the curing is caused because the local active group concentration is too high when the hydroxyl-terminated polyorganosiloxane, the crosslinking agent and the catalyst are added at one time is avoided. However, in order to make it difficult for the crosslinking agent and the catalyst to undergo a crosslinking reaction with the polyorganosiloxane and cure during the sealed storage, it is necessary to effectively fill the gap between the reactive groups of the crosslinking agent, the catalyst, and the hydroxyl-terminated polyorganosiloxane with the diluent, and therefore the amount of the diluent to be added needs to be kept at a certain amount or more; in addition, during actual use, the volatilization of the diluent needs a certain time, the formation of the coating needs an organic silicon coating with a certain concentration, and in order to avoid the problem that the time for forming the coating is too long or the coating with good performance is difficult to form, the addition amount of the diluent is not too large, so that the amount of the diluent must be strictly controlled reasonably, and meanwhile, the difficulty is increased for the actual operation due to the step-by-step implementation of experiments.
Therefore, there is a need to develop an improved silicone coating and a method for preparing the same, which can ensure good coating properties and also ensure that the properties do not decrease after long-term storage.
Disclosure of Invention
It is an object of the present application to provide a silicone coating.
It is another object of the present application to provide a method of preparing a silicone coating.
In one aspect, the silicone coating provided by the present application includes 25-35 parts by weight of alpha, omega-dihydroxy polysiloxane, 1-3 parts by weight of hydroxy silicone oil, 1-3 parts by weight of n-dodecyl trimethoxy silane, 15-25 parts by weight of ground calcium carbonate, 3-5 parts by weight of nano calcium carbonate, 1-3 parts by weight of fumed silica, 0.1-3 parts by weight of pigment, 30-40 parts by weight of diluent, 0.1-3 parts by weight of molecular sieve, 2-5 parts by weight of cross-linking agent, 0.1-3 parts by weight of catalyst, 0.1-3 parts by weight of vinyl trimethoxy silane, 0.1-3 parts by weight of adhesion promoter, and 0.1-3 parts by weight of coupling agent.
Alternatively, the viscosity of the α, ω -dihydroxypolysiloxane is from 2000 mPas to 20000 mPas at 25 ℃.
Alternatively, the α, ω -dihydroxypolysiloxane consists of an α, ω -dihydroxypolysiloxane having a viscosity at 25 ℃ of 2000 mPas and of 20000 mPas in a weight ratio of 1:1.5 to 1:2.5, preferably 1:2.
Alternatively, the weight ratio of vinyltrimethoxysilane to molecular sieve is in the range of 1:1 to 1:2, preferably 1:2.
Optionally, the specific surface area of the fumed silica is 150-400m2G, preferably 200-260m2/g。
Alternatively, the diluents employed in the present application are those commonly used in the art, preferably mineral spirits.
Alternatively, the crosslinking agent employed herein is one commonly used in the art, preferably methyltributanone oxime silane.
Alternatively, the catalyst employed herein is a catalyst commonly used in the art, preferably dibutyltin dilaurate.
Optionally, the adhesion promoter employed herein is a polyether-based alkoxysilane.
Alternatively, the coupling agent used in the present application is a coupling agent commonly used in the art, preferably silane coupling agent KH 550.
Optionally, the pigment used in the present application is one or more of carbon black, iron oxide red and titanium dioxide.
In another aspect, a method of preparing a silicone coating is provided that includes the steps of: weighing the components in parts by weight; uniformly mixing alpha, omega-dihydroxy polysiloxane, hydroxyl silicone oil and n-dodecyl trimethoxy silane in a kneader, adding heavy calcium carbonate, nano calcium carbonate and fumed silica, heating, stirring and vacuumizing for 3-5 hours, and keeping the temperature of the mixture at 140-160 ℃ and the vacuum degree at 0.09Mpa in the stirring process to obtain the base adhesive; and uniformly mixing the base glue and the pigment, adding the mixture into a dispersion machine, adding a diluent, a molecular sieve and a crosslinking agent, stirring for 5-10min, adding a catalyst, vinyl trimethoxy silane and a tackifier, stirring for 10-20min, and discharging to obtain the organic silicon coating.
Optionally, the fumed silica is baked at 105 ℃ for 1 hour before adding the fumed silica.
Optionally, the molecular sieve is baked at 105 ℃ for 1 hour before adding the molecular sieve.
Alternatively, the α, ω -dihydroxypolysiloxane, the hydroxy silicone oil, and the n-dodecyltrimethoxysilane may be mixed in a manner conventional in the art, such as by using a kneader.
Alternatively, the base gum can be uniformly mixed with the pigment using a grinding means and a grinding apparatus commonly used in the art.
The present application achieves water removal by combining chemical and physical methods to control the number of hydroxyl groups in the coating system. Particularly, the vinyl trimethoxy silane and the molecular sieve with good adsorption are jointly used for removing chemically bound water on the reinforcing filler and free hydroxyl in a system, so that the failure caused by the cross-linking reaction of a cross-linking agent and the hydroxyl in the system in the sealing and storing process is avoided, and the storage stability of the product is improved; meanwhile, adhesion of the coating can be improved by adding a tackifier and a coupling agent.
The organic silicon coating prepared by the application has the advantages of short curing time, less surface drying/actual drying time, strong adhesive force and good storage stability.
Detailed Description
Embodiments of the present application are described below by way of examples, and it should be appreciated by those skilled in the art that these specific examples merely illustrate selected embodiments for achieving the purposes of the present application and are not intended to limit the technical solutions. Modifications of the technical solutions of the present application in combination with the prior art are obvious from the teachings of the present application and fall within the protection scope of the present application.
The materials used in the following examples, except where noted, are commercially available; the equipment used, except where noted, is conventional in the art.
Example 1:
firstly, 10.8 parts by weight of alpha, omega-dihydroxy polysiloxane with the viscosity of 2000 mPas, 19.5 parts by weight of alpha, omega-dihydroxy polysiloxane with the viscosity of 20000 mPas, 1.3 parts by weight of hydroxyl silicone oil and 1.2 parts by weight of n-dodecyl trimethoxy silane are added into a kneader and kneaded evenly; then 22.1 parts by weight of heavy calcium carbonate, 4.5 parts by weight of nano calcium carbonate and 2.6 parts by weight of fumed silica are added (the fumed silica is baked for 1 hour at 105 ℃ before use); heating, vacuumizing and stirring for 3-5 h, sealing for later use, and keeping the temperature of the rubber material at 160 ℃ and the vacuum degree of 0.09Mpa in the stirring process to obtain the base rubber.
And then, grinding the prepared base adhesive and 0.2 part by weight of pigment on a three-roll mill, uniformly putting the ground base adhesive and the pigment into a high-speed dispersion machine, adding 30.4 parts by weight of solvent oil, 0.6 part by weight of molecular sieve (baking the molecular sieve for 1 hour at 105 ℃ before use) and 3.6 parts by weight of methyl tributyrinoxime silane, stirring the mixture at a high speed for 5 to 10 minutes, adding 0.1 part by weight of dibutyltin dilaurate, 1.2 parts by weight of vinyl trimethoxy silane, 0.7 part by weight of tackifier and 1.2 parts by weight of silane coupling agent KH550, and stirring the mixture for 10 to 30 minutes to obtain the organic silicon coating.
Example 2:
firstly, 10.7 parts by weight of alpha, omega-dihydroxy polysiloxane with the viscosity of 2000 mPas, 19.2 parts by weight of alpha, omega-dihydroxy polysiloxane with the viscosity of 20000 mPas, 1.3 parts by weight of hydroxyl silicone oil and 1.2 parts by weight of n-dodecyl trimethoxy silane are added into a kneader and kneaded evenly; then 21.8 parts by weight of heavy calcium carbonate, 4.4 parts by weight of nano calcium carbonate and 2.5 parts by weight of fumed silica are added (the fumed silica is baked for 1 hour at 105 ℃ before use); heating, vacuumizing and stirring for 3-5 h, sealing for later use, and keeping the temperature of the rubber material at 160 ℃ and the vacuum degree of 0.09Mpa in the stirring process to obtain the base rubber.
Then, the base rubber prepared above and 0.2 weight part of pigment are ground on a three-roll mill, evenly put into a high-speed dispersion machine, added with 30.1 weight parts of solvent oil, 1.2 weight parts of molecular sieve (baking the molecular sieve for 1 hour at 105 ℃ before use) and 3.6 weight parts of methyl tributyrinoxime silane, stirred at high speed for 5-10min, then added with 0.1 weight part of dibutyltin dilaurate, 1.2 weight parts of vinyl trimethoxy silane, 0.7 weight part of tackifier and 1.8 weight parts of silane coupling agent KH550, stirred for 10-30min, and the product is obtained.
Example 3:
firstly, 10 parts by weight of alpha, omega-dihydroxy polysiloxane with the viscosity of 2000 Pa.s, 20 parts by weight of alpha, omega-dihydroxy polysiloxane with the viscosity of 20000 mPa.s, 1.3 parts by weight of hydroxyl silicone oil and 1.2 parts by weight of n-dodecyl trimethoxy silane are added into a kneader and kneaded evenly; then 21.8 parts by weight of heavy calcium carbonate, 4.3 parts by weight of nano calcium carbonate and 2.5 parts by weight of fumed silica (fumed silica is baked for 1 hour at 105 ℃ before use); heating, vacuumizing and stirring for 3-5 h, sealing for later use, and keeping the temperature of the rubber material at 160 ℃ and the vacuum degree of 0.09Mpa in the stirring process to obtain the base rubber.
And then, grinding the prepared base adhesive and 0.2 part by weight of pigment on a three-roll machine, uniformly putting the ground base adhesive and the pigment into a planetary stirring kettle, adding 30.1 parts by weight of solvent oil, 1.8 parts by weight of molecular sieve (baking the molecular sieve for 1 hour at 105 ℃ before use) and 3.6 parts by weight of methyl tributyrinoxime silane, stirring at a high speed for 5-10min, adding 0.1 part by weight of dibutyltin dilaurate, 1.2 parts by weight of vinyl trimethoxy silane, 0.7 part by weight of tackifier and 1.2 parts by weight of silane coupling agent KH550, and stirring for 10-30min to obtain the adhesive.
Comparative example 1:
prepared in the same manner as in example 3 except that vinyltrimethylsilane and molecular sieve were not used.
Comparative example 2:
prepared in the same manner as in example 3, except that no coupling agent and tackifier were added.
The curing conditions and test protocol were as follows:
the organic silicon coating prepared in the above examples and comparative examples is coated on the surface of a tinplate sheet according to the sheet-making standard GB/T1927-92, the sheet is cured for 24 hours at room temperature, and the prepared test piece with uniform coating is tested according to the national standard for various performances.
The silicone coatings prepared in the above examples and comparative examples were stored in a sealed condition at 23 ℃ for 30 days, and then the adhesion of the coatings was evaluated.
The specific test results are shown in table 1 below.
TABLE 1
As can be seen from the results in Table 1, the paint of example 1 showed little sedimentation, as measured by the sedimentation according to the standard GB/T6753.3-1986, whereas the paints of examples 2 and 3 did not show any abnormalities. It is shown that the storage properties of the coating are better as the amount of molecular sieve in examples 2 and 3 is gradually increased, while the amount of vinyltrimethoxysilane is constant. In addition, when the amount of vinyltrimethoxysilane is constant, as the amount of the molecular sieve in example 2 and example 3 is gradually increased, the surface drying/tack-free time of the coating is gradually reduced. It is also seen that the coating of comparative example 1, which is completely free of vinyltrimethoxysilane and molecular sieve, delaminates significantly and the tack-free/tack-free time is greatly retarded. These all show well that the addition of vinyltrimethoxysilane and molecular sieves effectively scavenge hydroxyl groups in the system and contribute to the storage stability of the coating.
Further, when the amount of the tackifier was constant, the viscosity of examples 1, 2 and 3 increased with the addition of the silane coupling agent KH550, and the adhesion of the coating was increasingly good. It can be seen that the silane coupling agent KH550 and the tackifier have a great improvement effect on the tackifying performance of the coating, while the viscosity and adhesion are significantly reduced in comparative example 2 because the silane coupling agent KH550 and the tackifier are not added at all.
In conclusion, comparative example 1 and comparative example 2 further show that the addition of vinyltrimethoxysilane and a molecular sieve has a great effect of improving the storage property of the coating, and the silane coupling agent KH550 and the adhesion promoter can effectively promote the tackifying property of the coating. Meanwhile, the results of example 3 also show that the vinyl trimethoxy silane, the molecular sieve, the silane coupling agent KH550 and the adhesion promoter contained simultaneously have good synergistic effect on the performance of the coating.
The foregoing is considered as illustrative of the preferred embodiments of the present application and is not intended to limit the present application in any way or manner. Those skilled in the art should, however, appreciate that many modifications, adaptations, and variations are possible in light of the above teaching without departing from the scope of the present invention; meanwhile, any equivalent changes, modifications and evolutions of the above embodiments according to the essential technology of the present application are within the scope of the present application defined by the claims.
Claims (9)
1. An organosilicon coating comprises 25-35 parts by weight of alpha, omega-dihydroxypolysiloxane, 1-3 parts by weight of hydroxyl silicone oil, 1-3 parts by weight of n-dodecyl trimethoxy silane, 15-25 parts by weight of ground calcium carbonate, 3-5 parts by weight of nano calcium carbonate, 1-3 parts by weight of fumed silica, 0.1-3 parts by weight of pigment, 30-40 parts by weight of diluent, 0.1-3 parts by weight of molecular sieve, 2-5 parts by weight of cross-linking agent, 0.1-3 parts by weight of catalyst, 0.1-3 parts by weight of vinyl trimethoxy silane, 0.1-3 parts by weight of tackifier and 0.1-3 parts by weight of coupling agent.
2. The silicone coating of claim 1, wherein the viscosity of the α, ω -dihydroxy polysiloxane is from 2000 mPa-s to 20000 mPa-s at 25 ℃.
3. The silicone coating according to claim 1, wherein the α, ω -dihydroxypolysiloxane consists of α, ω -dihydroxypolysiloxanes having viscosities of 2000 mPa-s and 20000 mPa-s at 25 ℃ in a weight ratio of 1:1.5 to 1:2.5, preferably 1:2.
4. The silicone coating of claim 1, wherein the weight ratio of vinyltrimethoxysilane to molecular sieve is in the range of 1:1 to 1:2, preferably 1:2.
5. The silicone coating as set forth in claim 1, wherein the fumed silica has a specific surface area of 150-400m2G, preferably 200-260m2/g。
6. The silicone coating of claim 1, wherein the diluent is selected from the group consisting of mineral spirits; the cross-linking agent is selected from methyl tributyl ketoxime silane; the catalyst is selected from dibutyltin dilaurate; the tackifier is selected from polyether alkoxy silane; the coupling agent is selected from a silane coupling agent KH550, and the pigment is selected from one or more of carbon black, iron oxide red and titanium dioxide.
7. A method of preparing the silicone coating of any of claims 1-6, comprising the steps of:
weighing the components in parts by weight;
uniformly mixing alpha, omega-dihydroxy polysiloxane, hydroxyl silicone oil and n-dodecyl trimethoxy silane in a kneader, adding heavy calcium carbonate, nano calcium carbonate and fumed silica, heating, stirring and vacuumizing for 3-5 hours, and keeping the temperature of the mixture at 140-160 ℃ and the vacuum degree at 0.09Mpa in the stirring process to obtain the base adhesive;
and uniformly mixing the base glue and the pigment, adding the mixture into a dispersion machine, adding a diluent, a molecular sieve and a crosslinking agent, stirring for 5-10min, adding a catalyst, vinyl trimethoxy silane and a tackifier, stirring for 10-20min, and discharging to obtain the organic silicon coating.
8. The method of claim 7, wherein the fumed silica is baked at 105 ℃ for 1 hour prior to adding the fumed silica.
9. The method of claim 7, wherein the molecular sieve is baked at 105 ℃ for 1 hour prior to adding the molecular sieve.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117659862A (en) * | 2023-12-18 | 2024-03-08 | 北京和尔泰新材料科技有限公司 | High-temperature-resistant protective coating and preparation and use methods thereof |
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| CN117659862A (en) * | 2023-12-18 | 2024-03-08 | 北京和尔泰新材料科技有限公司 | High-temperature-resistant protective coating and preparation and use methods thereof |
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