CN111662428A - Self-curing modified organic fluorine-silicon antifouling resin and preparation method thereof - Google Patents
Self-curing modified organic fluorine-silicon antifouling resin and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6469—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having silicon
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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Abstract
The invention discloses a self-curing modified organic fluorine-silicon antifouling resin, which is formed by firstly synthesizing a silicon dioxide/polyethylene glycol/organic fluorine-silicon prepolymer from isocyanate, silicon dioxide/polyethylene glycol and hydroxypropyl fluorine-silicon oil under the action of dibutyltin dilaurate, and then absorbing air moisture by using the rest isocyanate to self-cure the prepolymer into a film; silane modified silicon dioxide and polyethylene glycol react to form a silicon dioxide/polyethylene glycol prefabricated object, excessive isocyanate is used as a chain extender, supersaturated silicon dioxide/polyethylene glycol/organic fluorine-silicon resin with an isocyanate structure is directly formed, a resin microphase separation structure is endowed, protein adhesion can be effectively inhibited, and thus adhesion of lipophilic fouling organisms is reduced, and meanwhile, moisture absorption in air can be realized through excessive isocyanate, and a film is formed through self-curing.
Description
Technical Field
The invention relates to the technical field of chemical materials suitable for ships and oceans, in particular to self-curing modified organic fluorine-silicon antifouling resin and a preparation method thereof.
Background
The consumed antifouling paint mainly adopts a large amount of antifouling agents as biocides to effectively inhibit the attachment of fouling organisms on the surface of a ship body, but most antifouling agents are heavy metal-containing compounds such as cuprous oxide and the like, are difficult to decompose in seawater, are easy to cause biological enrichment, and destroy the ecological environment. In order to effectively solve the problem, foreign coating companies represented by IP companies have developed fouling release type antifouling coatings based on the low surface energy and elastic characteristics of silicone materials, but the coatings are not suitable for use in low-speed ships because the protein adhesion property of silicone materials to inhibit fouling organisms is poor and adhesion conditions are easily created for the fouling organisms.
Aiming at the problems, the hydrophilic material has the characteristic of inhibiting protein adhesion, and can form a microphase separation structure to a certain extent by combining with the organic silicon material, thereby being beneficial to improving the surface protein adhesion resistance of the organic silicon. The main literature for designing silicone resin by using this principle is: chinese patent publication No. CN104877421A discloses a fluorosilicone modified acrylic antifouling paint containing polyethylene glycol and a preparation method thereof, which copolymerizes allyl glycol and acrylate to polyethylene glycol/acrylate, and then polycondenses polydimethylsiloxane oligomer and perfluoropolyether oligomer to form a film, so as to form a material with anti-protein adhesion, but the structural block contains a large amount of acrylate structures, which is not conducive to forming a microphase separation structure; chinese patent publication No. CN105219206A discloses a method for preparing silicone-modified acrylic hydrogel antifouling paint, which is to synthesize silicone-modified acrylic resin with acrylic silane ester and hydroxy silicone oil, although the side chain of acrylic silane has a certain hydrophilicity after hydrolysis, the difference with polyethylene glycol is large, and the requirement of protein adhesion resistance cannot be met, i.e., the technical scheme does not have a protein-resistant design structure; chinese patent publication No. CN105273600A discloses a method for preparing an organosilicon-modified polyurethane hydrogel antifouling paint, which uses polytetrahydrofuran ether or polyethylene glycol, polysiloxane diol, and dihydroxy methyl butyric acid as structural units, and then synthesizes organosilicon-modified polyurethane resin through butanediol and isocyanate, chinese patent publication No. CN106280969A discloses a method for preparing a marine antifouling paint based on modified polyether fluorosilicone oil with low surface energy, wherein polyether diol and diisocyanate are used to synthesize polyether polyurethane prepolymer first, meanwhile, a silane coupling agent KH550 and terminal hydroxyl fluorosilicone oil are used to synthesize terminal aminopropyl fluorosilicone oil, and finally, the polyether polyurethane prepolymer and the terminal hydroxyl fluorosilicone oil are reacted to synthesize the modified polyether fluorosilicone oil, and the reaction steps of the two patents are long and are both multi-component curing designs; the mechanical science research institute reports that a polyurethane prepolymer is synthesized in advance by polytetrahydrofuran ether and isocyanate, then a chain extender binary aromatic ammonia is used for further chain extension to synthesize a low-surface-energy polyurethane elastic material with high strength, an antifouling agent is added in an auxiliary manner, and the antifouling material is applied to a coating, so that the actual antifouling performance is less than 9 months, and a large difference still exists between the antifouling performance and the application.
Therefore, the problem which is mainly solved at present is to develop an antifouling resin which inhibits protein adhesion and effectively reduces the adhesion of lipophilic fouling organisms through a hydrophilic-hydrophobic microphase separation structure so as to inhibit the adhesion of the fouling organisms, and to prepare the antifouling resin through a simple process.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a self-curing modified organic fluorine-silicon antifouling resin and a preparation method thereof, wherein the antifouling resin can be prepared by a simple preparation process, and the antifouling resin inhibits protein adhesion through a hydrophilic-hydrophobic microphase separation structure, effectively reduces the adhesion of lipophilic fouling organisms, and realizes the inhibition of the adhesion of the fouling organisms.
In order to achieve the purpose, the invention adopts the specific scheme that:
a self-curing modified organic fluorine-silicon antifouling resin is prepared by firstly synthesizing a silicon dioxide/polyethylene glycol/organic fluorine-silicon prepolymer from isocyanate, silicon dioxide/polyethylene glycol and hydroxypropyl fluorosilicone oil under the action of dibutyltin dilaurate, and then utilizing the rest of isocyanate to absorb air moisture for self-curing to form a film, wherein the molecular structure of the antifouling resin is
Wherein R is amino or epoxy, and R' is methylene.
Further, the polyethylene glycol is any one or more of polyethylene glycol with the molecular weight of 200-1800.
Further, the hydroxypropyl fluorosilicone oil is any one or more of the viscosity of 1000-5000.
Further, the isocyanate is one or two of isophorone diisocyanate and hexamethylene diisocyanate.
A preparation method of self-curing modified organic fluorine-silicon antifouling resin comprises the following steps: premixing 0.2-1 g of silane modified nano-silica dispersion liquid and 2-10 g of polyethylene glycol for 10min to obtain a silica/polyethylene glycol premix, then adding the silica/polyethylene glycol premix, 10-40 g of hydroxypropyl fluorosilicone oil, 2-5 g of xylene and 0.1-0.2 g of dibutyltin dilaurate into a four-mouth flask, uniformly mixing, and heating to 75 +/-3 ℃ to obtain a mixed solution; and (3) filling 3-6 g of isocyanate into a constant-pressure dropping funnel, slowly dropping the isocyanate into the mixed solution for 1-1.5 h, and keeping the temperature for 3-4 h to obtain the antifouling resin.
Further, the specific preparation method of the silane modified nano-silica dispersion liquid comprises the following steps: mixing 0.1g of silane ester with 10g of nano-silica dispersion liquid with the concentration of 10%, heating to 50 +/-3 ℃, and reacting for 1h to obtain the silane modified nano-silica dispersion liquid.
Further, the silane ester is one or two of KH550 and KH 560.
Further, the particle size of the silicon dioxide in the nano silicon dioxide dispersion liquid is 50-100 nm.
The hydroxypropyl fluorosilicone oil is used as a hydrophobic chain segment, and effectively inhibits the attachment of hydrophilic fouling organisms.
The silane modified silicon dioxide has the function of providing an active group to react with polyethylene glycol, so that the strength of the polyethylene glycol is improved.
The reason for the last slow dropwise addition of isocyanate is: the modified polyethylene glycol and the hydroxypropyl fluorosilicone oil are used as a connecting chain extender, so that the resin has a microphase separation structure.
Has the advantages that:
the antifouling resin adopts polyethylene glycol as a hydrophilic component, silane modified silicon dioxide as a polyethylene glycol reinforcing agent, and hydroxypropyl fluorosilicone oil as a hydrophobic component; the preparation method comprises the steps of reacting silicon dioxide with a small amount of silane ester to form silane modified silicon dioxide, reacting the silane modified silicon dioxide with a hydrophilic component-polyethylene glycol to form a silicon dioxide/polyethylene glycol prefabricated product, and directly forming supersaturated silicon dioxide/polyethylene glycol/organic fluorine-silicon resin with an isocyanate structure by taking excessive isocyanate as a chain extender, so that a microphase separation structure is endowed to the resin, protein adhesion can be effectively inhibited, adhesion of lipophilic fouling organisms is reduced, and meanwhile, moisture absorption in air can be realized, and a film is formed through self-curing due to excessive isocyanate.
Drawings
FIG. 1 is a schematic diagram showing the synthesis of a modified organofluorosilicone antifouling resin according to the present invention.
FIG. 2 is a microscope photograph of a Navicula attached with an organofluorosilicone resin prepared in the prior art.
FIG. 3 is a microscopic view of the modified organofluorosilicone antifouling resin prepared in example 1 after attachment of Navicula.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, belong to the scope of the present invention.
A self-curing modified organic fluorine-silicon antifouling resin is prepared by firstly synthesizing a silicon dioxide/polyethylene glycol/organic fluorine-silicon prepolymer from isocyanate, silicon dioxide/polyethylene glycol and hydroxypropyl fluorosilicone oil under the action of dibutyltin dilaurate, and then utilizing the rest of isocyanate to absorb air moisture for self-curing to form a film, wherein the molecular structure of the antifouling resin is
Wherein R is amino or epoxy, R' is methylene, m represents the number of structural repetition in the molecular structure of the hydroxypropyl fluorosilicone oil, and the number of m is limited by the viscosity of the hydroxypropyl fluorosilicone oil because the measurement of the molecular weight of the hydroxypropyl fluorosilicone oil is difficult, and the selected hydroxypropyl fluorosilicone oil is any one or more of the viscosity of 1000-5000; n represents the number of structural repeats in a polyethylene glycol molecular structure, the number of n is limited by adopting molecular weight, and the selected polyethylene glycol is any one or more of polyethylene glycol with the molecular weight of 200-1800; denotes F or other groups.
A preparation method of self-curing modified organic fluorine-silicon antifouling resin comprises the following steps: mixing 0.1g of silane ester with 10g of nano-silica dispersion liquid with the concentration of 10%, heating to 50 +/-3 ℃, and reacting for 1h to obtain silane modified nano-silica dispersion liquid; premixing 0.2-1 g of silane modified nano-silica dispersion liquid and 2-10 g of polyethylene glycol for 10min to obtain a silica/polyethylene glycol premix, then adding the silica/polyethylene glycol premix, 10-40 g of hydroxypropyl fluorosilicone oil, 2-5 g of xylene and 0.1-0.2 g of dibutyltin dilaurate into a four-mouth flask, uniformly mixing, and heating to 75 +/-3 ℃ to obtain a mixed solution; and (2) filling 3-6 g of isocyanate into a constant-pressure dropping funnel, slowly dropping the isocyanate into the mixed solution for 1-1.5 hours, and keeping the temperature for 3-4 hours to obtain the antifouling resin, wherein a synthetic circuit diagram of the antifouling resin is shown in figure 1, wherein R represents amino or epoxy, R 'represents alkyl, and R' represents methylene.
The isocyanate is one or two of isophorone diisocyanate and hexamethylene diisocyanate. The silane ester is one or two of KH550 and KH 560. The particle size of the silicon dioxide in the nano silicon dioxide dispersion liquid is 50-100 nm.
Example 1
A preparation method of self-curing modified organic fluorine-silicon antifouling resin comprises the following steps: mixing 0.1g of KH550 with 10g of nano-silica dispersion with the concentration of 10%, heating to 50 +/-3 ℃, and reacting for 1h to obtain silane modified nano-silica dispersion; premixing 0.2g of silane modified nano-silica dispersion liquid and 2g of polyethylene glycol 200 for 10min to obtain a silica/polyethylene glycol premix, then adding the silica/polyethylene glycol premix, 10g of hydroxypropyl fluorosilicone oil 1000, 2g of xylene and 0.1g of dibutyltin dilaurate into a four-mouth flask, uniformly mixing, and heating to 75 +/-3 ℃ to obtain a mixed solution; 3g of isophorol diisocyanate is filled into a constant pressure dropping funnel, and then is slowly dropped into the mixed solution for 1h, and the temperature is kept for 3h, so that the antifouling resin is obtained.
The antifouling properties of the antifouling resin prepared according to the present invention were verified by using navicula as an object of study, wherein fig. 2 shows the organofluorosilicone resin prepared according to the prior art, fig. 3 shows the antifouling resin prepared according to example 1, and it can be seen from the figure that many adhering spots exist on the surface in fig. 2 and only a few adhering spots exist on the surface in fig. 3, and thus the antifouling resin prepared according to the present invention has excellent antifouling properties.
Example 2
A preparation method of self-curing modified organic fluorine-silicon antifouling resin comprises the following steps: mixing 0.1g of KH560 with 10g of nano-silica dispersion with the concentration of 10%, heating to 50 +/-3 ℃, and reacting for 1h to obtain silane modified nano-silica dispersion; premixing 0.4g of silane modified nano-silica dispersion liquid and 5g of polyethylene glycol 600 for 10min to obtain a silica/polyethylene glycol premix, then adding the silica/polyethylene glycol premix, 20g of hydroxypropyl fluorosilicone oil 3000, 4g of xylene and 0.12g of dibutyltin dilaurate into a four-mouth flask, uniformly mixing, and heating to 75 +/-3 ℃ to obtain a mixed solution; 4g of hexamethylene diisocyanate is filled into a constant pressure dropping funnel, and then slowly dropped into the mixed solution for 1.2h, and the temperature is kept for 3h, so that the antifouling resin is obtained.
Example 3
A preparation method of self-curing modified organic fluorine-silicon antifouling resin comprises the following steps: mixing 0.1g of KH550 with 10g of nano-silica dispersion with the concentration of 10%, heating to 50 +/-3 ℃, and reacting for 1h to obtain silane modified nano-silica dispersion; premixing 0.8g of silane modified nano-silica dispersion liquid and 10g of polyethylene glycol 1000 for 10min to obtain a silica/polyethylene glycol premix, then adding the silica/polyethylene glycol premix, 30g of hydroxypropyl fluorosilicone oil 5000, 5g of xylene and 0.15g of dibutyltin dilaurate into a four-mouth flask, uniformly mixing, and heating to 75 +/-3 ℃ to obtain a mixed solution; 6g of isophorol diisocyanate is filled into a constant pressure dropping funnel, and then is slowly dropped into the mixed solution for 1.5h, and the temperature is kept for 3.5h, so that the antifouling resin is obtained.
The antifouling resin prepared by the invention can effectively reduce the adhesion of lipophilic fouling organisms, and the static actual antifouling performance of the antifouling resin is more than 7 months proved by practice.
The foregoing is merely a preferred embodiment of the invention and is not to be construed as limiting the invention in any way. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A self-curing modified organic fluorine-silicon antifouling resin is characterized in that the antifouling resin is prepared by firstly synthesizing silicon dioxide/polyethylene glycol from isocyanate, silicon dioxide/polyethylene glycol and hydroxypropyl fluorosilicone oil under the action of dibutyltin dilaurateThe molecular structure of the antifouling resin is that the glycol/organic fluorine-silicon prepolymer is formed by self-curing into a film by absorbing air moisture with the residual isocyanate
Wherein R is amino or epoxy, and R' is methylene.
2. The self-curing modified organofluorosilicone antifouling resin according to claim 1, wherein: the polyethylene glycol is any one or more of polyethylene glycol with the molecular weight of 200-1800.
3. The self-curing modified organofluorosilicone antifouling resin according to claim 1, wherein: the hydroxypropyl fluorosilicone oil is any one or more of the viscosity of 1000-5000.
4. The self-curing modified organofluorosilicone antifouling resin according to claim 1, wherein: the isocyanate is one or two of isophorone diisocyanate and hexamethylene diisocyanate.
5. A preparation method of self-curing modified organic fluorine-silicon antifouling resin is characterized by comprising the following steps: premixing 0.2-1 g of silane modified nano-silica dispersion liquid and 2-10 g of polyethylene glycol for 10min to obtain a silica/polyethylene glycol premix, then adding the silica/polyethylene glycol premix, 10-40 g of hydroxypropyl fluorosilicone oil, 2-5 g of xylene and 0.1-0.2 g of dibutyltin dilaurate into a four-mouth flask, uniformly mixing, and heating to 75 +/-3 ℃ to obtain a mixed solution; and (3) filling 3-6 g of isocyanate into a constant-pressure dropping funnel, slowly dropping the isocyanate into the mixed solution for 1-1.5 h, and keeping the temperature for 3-4 h to obtain the antifouling resin.
6. The preparation method of the self-curing modified organic fluorine-silicon antifouling resin as claimed in claim 5, wherein the specific preparation method of the silane modified nano-silica dispersion liquid comprises the following steps: mixing 0.1g of silane ester with 10g of nano-silica dispersion liquid with the concentration of 10%, heating to 50 +/-3 ℃, and reacting for 1h to obtain the silane modified nano-silica dispersion liquid.
7. The preparation method of the self-curing modified organic fluorine-silicon antifouling resin according to claim 6, wherein the preparation method comprises the following steps: the silane ester is one or two of KH550 and KH 560.
8. The preparation method of the self-curing modified organic fluorine-silicon antifouling resin according to claim 6, wherein the preparation method comprises the following steps: the particle size of the silicon dioxide in the nano silicon dioxide dispersion liquid is 50-100 nm.
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| CN114773996A (en) * | 2022-04-01 | 2022-07-22 | 哈尔滨工程大学 | Super-hydrophobic coating with anti-icing function and preparation method thereof |
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