Surface coating as well as preparation method and application thereof

Abstract

The invention discloses a surface coating as well as a preparation method and application thereof, the surface coating comprises a polyaniline particle surface layer and an organic silicon resin substrate layer, and the preparation method comprises the following steps: applying a polyaniline particle dispersion liquid to the surface of pre-cured organic silicon resin, and drying to obtain the surface coating. The mechanical anchoring effect of the functionalized organic silicon resin and the sea urchin-like polyaniline particles is utilized, so that the composite coating can still keep the adhesion effect with the base material and the micro-nano structure of the coating under the action of external force, high durability is achieved, and the composite coating has good application prospects in the fields of base material self-cleaning and icing resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and in particular relates to a surface coating and a preparation method and application thereof. Background Art

[0002] Common substrates such as concrete and wood are susceptible to factors such as freeze-thaw, water penetration, and ion corrosion in natural environments, which can damage the substrate and ultimately reduce its service life. In response to this situation, super-hydrophobic coating protection for such substrates in special environments is currently becoming a major research hotspot. As a physical shield, super-hydrophobic coating protection can effectively inhibit the penetration of corrosive substances, improve coating durability, reduce the long-term maintenance cost of the substrate, and to a certain extent delay the destruction of the substrate.

[0003] Bionic super-hydrophobic surfaces have gained wide attention in the research of substrate surface protection due to their excellent water repellency (water contact angle > 150°, rolling angle < 10°), and have developed rapidly in the fields of self-cleaning, anti-icing, anti-freeze-thaw and corrosion protection. For super-hydrophobic surfaces, low surface energy materials and micro-nano rough structures are two essential prerequisites, so the main method for preparing bionic super-hydrophobic surfaces is still to compound low-surface energy "adhesives" with "hydrophobic particles". The combination of traditional adhesives and hydrophobic particles often faces two problems: on the one hand, due to their low surface energy requirements, adhesives have poor adhesion to the substrate, resulting in coating peeling when the material faces external influences such as mechanical or chemical wear; on the other hand, there are problems such as incompatibility between low-surface energy adhesive materials and hydrophobic particles during the composite process, and stratification and abrasion are prone to occur after long-term physical and chemical damage, which ultimately leads to the disappearance of the super-hydrophobic properties of the composite coating and failure of durability. Summary of the invention

[0004] Purpose of the invention: The purpose of the present invention is to provide a highly durable super-hydrophobic surface coating with high compatibility of resin particles and regulation of bionic microstructure; another purpose of the present invention is to provide a preparation method and application of the surface coating.

[0005] Technical solution: The surface coating of the present invention comprises a polyaniline particle surface layer and a silicone resin base layer, and the mass ratio of the polyaniline particles to the silicone resin is 1 to 1.5:2.

[0006] Preferably, the particle size of the polyaniline particles is 1 to 5 μm.

[0007] The preparation method of the surface coating of the present invention comprises the following steps: applying a polyaniline particle dispersion to the surface of a pre-cured silicone resin, and obtaining the surface coating after drying.

[0008] Preferably, the specific preparation method is to apply a silicone resin solution to the surface of a substrate and perform a pre-curing treatment; polyaniline particles are dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline particle dispersion, and then the polyaniline particle dispersion is applied to the surface of the substrate after the resin pre-curing treatment, and a surface coating is obtained after drying.

[0009] Preferably, the preparation method of the polyaniline particles is: weigh p-toluenesulfonic acid and aniline, dissolve them in ethanol, and disperse them by ultrasonication; dissolve ammonium persulfate in pure water and mix it with the above solution, stir it, let it stand, and dry it to obtain the polyaniline particles.

[0010] Preferably, the molar ratio of p-toluenesulfonic acid, ammonium persulfate and aniline is 0.9-1.1:0.9-1.1:4.5-5.5, and the volume ratio of ethanol to pure water is 3.5-4.5:5.5-6.5.

[0011] Preferably, the concentration of p-toluenesulfonic acid in ethanol is 34.4-54.1 g / cm 3 .

[0012] Preferably, the concentration of aniline in ethanol is 158.0-228.2 g / cm 3 .

[0013] Preferably, the concentration of ammonium persulfate in pure water is 18.6-29.3 g / cm 3 .

[0014] Preferably, the ultrasonic dispersion time is 8 to 10 minutes, the stirring time is 5 to 10 minutes, the stirring reaction temperature is 20 to 25° C., and the stirring reaction time is 4 to 6 hours.

[0015] Preferably, the polyaniline particles are dried in an oven at 60 to 80° C. for 8 to 12 hours.

[0016] Preferably, the preparation method of the silicone resin is: adding isocyanate solution dropwise to polydimethylsiloxane solution, stirring at room temperature for reaction; heating to 70-90°C after stirring for 4-6 hours, and adding A solution to obtain silicone resin under catalytic reaction, wherein A includes at least one of disulfide segment and fluorinated benzidine.

[0017] Preferably, the preparation method of the silicone resin is: adding isocyanate solution dropwise to polydimethylsiloxane solution, stirring at room temperature for reaction; heating to 70-90° C. after stirring for 4-6 hours, and adding a mixed solution of disulfide segment and fluorinated benzidine to obtain the silicone resin under catalytic reaction.

[0018] Preferably, the molar ratio of the isocyanate to polydimethylsiloxane is 3:1 to 3.4:1, the molar ratio of the disulfide segment to polydimethylsiloxane is 0.9 to 1.2:1, and the molar ratio of the fluorinated benzidine to polydimethylsiloxane is 0.9 to 1.2:1.

[0019] Preferably, the disulfide segment is 4,4-diaminodiphenyl disulfide, and the fluorinated benzidine is 2,2-bis(trifluoromethyl)diaminobiphenyl.

[0020] Preferably, the molecular weight of the polydimethylsiloxane is 2500-5000 g / mol.

[0021] Preferably, the molecular weight of the polydimethylsiloxane is 2500, 3000 or 5000 g / mol.

[0022] Preferably, the solvent of the isocyanate solution and solution A is butyl acetate.

[0023] Preferably, the mass fraction of the polydimethylsiloxane solution is 30-40%, and the mass fraction of the isocyanate, the disulfide segment and the fluorinated benzidine in the butyl acetate solution is 10-20%.

[0024] Preferably, the isocyanate is isophorone diisocyanate.

[0025] Preferably, the catalytic reaction time is 3 to 5 hours.

[0026] Preferably, the catalyst for the catalytic reaction is dibutyltin dilaurate, and its mass fraction in the mixed butyl acetate solution is 0.5-1%.

[0027] Preferably, the method of applying the silicone resin solution to the substrate includes direct pouring, dripping, knife coating, brushing or spraying.

[0028] Preferably, the spraying concentration of the polyaniline in butyl acetate is 0.75-1.25 g / ml.

[0029] Preferably, the pre-curing temperature is 40-80° C., and the pre-curing time is 10-30 min.

[0030] Preferably, the mass fraction of the polyaniline particles in the polyaniline particle dispersion is 8-10%, and the dispersion used is butyl acetate.

[0031] Preferably, the polyaniline particles are dried at a temperature of 40 to 60° C. on the pre-cured surface, and the drying time is 2.5 to 3.5 hours.

[0032] The surface coating of the present invention is used in various substrates, including concrete, wood, glass and stainless steel plates.

[0033] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0034] (1) The present invention prepares a highly durable super-hydrophobic composite coating on the surface of a substrate, which is obtained by pre-curing a bottom layer of a multi-reversible bond organosilicon resin coating and spraying a bionic sea urchin-like polyaniline particle on the surface. The high adhesion of the substrate is achieved by multiple hydrogen bonds between the organosilicon resin and the surface of the substrate, and the overall compatibility of the composite coating is improved by multiple hydrogen bonds and π-π stacking between the sea urchin-like nanoparticles and the resin, so as to achieve strong mechanical anchoring of the particles and the resin. It can still maintain adhesion with the substrate and the micro-nano structure of the coating under the action of external force, and achieve high durability.

[0035] (2) By selecting the material ratio and controlling the above process, the composite coating regulated by the bionic microstructure prepared by the present invention exhibits excellent super-hydrophobic properties. It has the ability to repel various liquid droplets such as orange juice, milk, coffee, etc., can remove surface mud and sand stains under water flushing, and has good self-cleaning ability.

[0036] (3) The super-hydrophobic composite coating prepared by the present invention can withstand a series of chemical and physical durability tests, and the high durability of the composite coating is verified by sandpaper wear (the wear resistance distance of the coating under a load of 100 g with 1000 mesh sandpaper) and tape sticking. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a schematic diagram of the microscopic morphology of polyaniline in Example 1 of the present invention;

[0038] Figure 2 is an infrared schematic diagram of the silicone resin in Examples 1, 4, and 5 of the present invention;

[0039] Figure 3 This is a schematic diagram of preparing the composite coating in Example 1 of the present invention; 1-organic silicone resin layer, 2-polyaniline particles;

[0040] Figure 4 Schematic diagram of surface hydrophobic angle at different polyaniline spraying concentrations in Examples 6-8 of the present invention and Comparative Examples 2-3;

[0041] Figure 5 Schematic diagram showing the effect of the number of sandpaper polishing on the contact angle of the composite coating in Example 7 of the present invention;

[0042] Figure 6 It is a schematic diagram of the effect of the number of times the tape is applied on the contact angle of the composite coating in Example 7 of the present invention. DETAILED DESCRIPTION

[0043] The technical solution of the present invention is further described below in conjunction with embodiments and drawings.

[0044] Example 1

[0045] Embodiment 1 of the present invention provides a highly durable super-hydrophobic coating regulated by bionic microstructure on a concrete surface and a preparation method thereof, comprising the following steps:

[0046] Preparation of polyaniline particles: 1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol and ultrasonicated for 10min. 5mmol aniline was dissolved in the above solution, mixed evenly, and 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanically stirred for 5min, and allowed to stand for 4h. The obtained solution was centrifuged at 8000r / min for 10min, the sediment was obtained, and dried at 80℃ for 8h to obtain super hydrophobic sea urchin-like polyaniline particles. The microscopic morphology of sea urchin-like polyaniline particles is as follows: Figure 1 The obtained polyaniline surface presents a thorny sea urchin-like morphology, and its surface water contact angle is 153.8±1°, achieving super hydrophobicity.

[0047] Preparation of silicone resin: 3.37mmol of isophorone diisocyanate was dissolved in 10ml of butyl acetate and placed in a three-necked flask. 1mmol of amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml of butyl acetate and added dropwise to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer (PDSF). Figure 2 The reaction temperature was raised to 80°C, 1 mmol of disulfide segment and 1 mmol of fluorinated benzidine were dissolved in 20 ml of butyl acetate, and the above prepolymer solution was added, and the reaction was carried out for 4 hours in the presence of 0.5% by mass of dibutyltin dilaurate to obtain a multi-reversible functional bond silicone resin.

[0048] Preparation of highly durable super-hydrophobic coating regulated by bionic microstructure: functionalized silicone resin solution is spin-coated on the surface of concrete substrate for pre-curing; polyaniline particles are dispersed in organic solvent under ultrasonic conditions to prepare polyaniline dispersion, and then the particle dispersion is sprayed on the surface of concrete substrate pre-cured with resin using a spray gun. The obtained coating is dried at room temperature 50°C for 3 hours, and a highly durable bionic super-hydrophobic composite coating can be obtained when the molecular weight of polydimethylsiloxane is 5000g / mol.

[0049] Example 2

[0050] Embodiment 2 of the present invention provides a highly durable super-hydrophobic coating regulated by bionic microstructure on a concrete surface and a preparation method thereof, comprising the following steps:

[0051] Preparation of polyaniline particles: 0.9 mmol p-toluenesulfonic acid was dissolved in 4 ml ethanol and ultrasonicated for 10 min. 4.5 mmol aniline was dissolved in the above solution, mixed evenly, and 0.9 mmol ammonium persulfate aqueous solution (6 ml) was added, mechanically stirred for 5 min, and allowed to stand for 4 h. The resulting solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the sediment was obtained and dried at 60 ° C for 8 h to obtain super hydrophobic sea urchin polyaniline particles.

[0052] Preparation of silicone resin: 3.1mmol isophorone diisocyanate was dissolved in 10ml butyl acetate and placed in a three-necked flask. 1mmol amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml butyl acetate and added to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer (PDSF). The reaction temperature was raised to 80°C, 0.9mmol disulfide segment and 0.9mmol fluorinated benzidine were dissolved in 20ml butyl acetate, and the above prepolymer solution was added. The reaction was carried out for 4h in the presence of 0.5% dibutyltin dilaurate by mass fraction to obtain a multi-reversible functional bond silicone resin.

[0053] Preparation of highly durable super-hydrophobic coating regulated by bionic microstructure: functionalized silicone resin solution is spin-coated on the surface of concrete substrate for pre-curing; polyaniline particles are dispersed in organic solvent under ultrasonic conditions to prepare polyaniline dispersion, and then the particle dispersion is sprayed on the surface of concrete substrate treated with resin pre-curing using a spray gun. The obtained coating is dried at room temperature of 50°C for 3 hours to obtain a highly durable bionic super-hydrophobic composite coating.

[0054] Example 3

[0055] Embodiment 3 of the present invention provides a highly durable super-hydrophobic coating regulated by bionic microstructure on a concrete surface and a preparation method thereof, comprising the following steps:

[0056] Preparation of polyaniline particles: 1.1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol and ultrasonicated for 10min. 5.5mmol aniline was dissolved in the above solution, mixed evenly, and 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanically stirred for 5min, and allowed to stand for 4h. The obtained solution was centrifuged at 8000r / min for 10min with aqueous solution, and the sediment was obtained and dried at 80℃ for 8h to obtain superhydrophobic sea urchin polyaniline particles.

[0057] Preparation of silicone resin: 3.4mmol isophorone diisocyanate was dissolved in 10ml butyl acetate and placed in a three-necked flask. 1mmol amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml butyl acetate and added to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer (PDSF). The reaction temperature was raised to 80°C, 1.2mmol disulfide segment and 1.2mmol fluorinated benzidine were dissolved in 20ml butyl acetate, and the above prepolymer solution was added. The reaction was carried out for 4h in the presence of 1% dibutyltin dilaurate by mass fraction to obtain a multi-reversible functional bond silicone resin.

[0058] Preparation of highly durable super-hydrophobic coating regulated by bionic microstructure: functionalized silicone resin solution is spin-coated on the surface of concrete substrate for pre-curing; polyaniline particles are dispersed in organic solvent under ultrasonic conditions to prepare polyaniline dispersion, and then the particle dispersion is sprayed on the surface of concrete substrate treated with resin pre-curing using a spray gun. The obtained coating is dried at room temperature of 50°C for 3 hours to obtain a highly durable bionic super-hydrophobic composite coating.

[0059] Example 4

[0060] Embodiment 4 of the present invention provides a highly durable super hydrophobic coating regulated by bionic microstructure on the surface of concrete without fluorine-containing segments and a preparation method thereof, comprising the following steps:

[0061] Preparation of polyaniline particles: 1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol and ultrasonicated for 10min. 5mmol aniline was dissolved in the above solution, mixed evenly, and 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanically stirred for 5min, and allowed to stand for 4h. The obtained solution was centrifuged at 8000r / min for 10min with aqueous solution, and the sediment was obtained and dried at 80℃ for 8h to obtain superhydrophobic sea urchin-like polyaniline particles.

[0062] Preparation of silicone resin: 3.37mmol of isophorone diisocyanate was dissolved in 10ml of butyl acetate and placed in a three-necked flask. 1mmol of amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml of butyl acetate and added dropwise to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer (PDS). Figure 2 The reaction temperature was raised to 80°C, 2 mmol of disulfide segment was dissolved in 20 ml of butyl acetate, and the above prepolymer solution was added, and the reaction was carried out for 4 hours in the presence of 0.5% by mass of dibutyltin dilaurate to obtain a multi-reversible functional bond silicone resin.

[0063] Preparation of highly durable bionic microstructure-regulated super-hydrophobic composite coating: Take the functionalized organic silicone resin solution and spin-coat it on the surface of the concrete substrate for pre-curing treatment; functional sea urchin super-hydrophobic particles are dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then the particle dispersion is sprayed onto the surface of the concrete substrate treated with resin pre-curing using a spray gun. The obtained coating is dried at 50°C for 3h, and a highly durable bionic super-hydrophobic composite coating is obtained without fluorine-containing silicone-based resin.

[0064] Example 5

[0065] Embodiment 5 of the present invention provides a highly durable super-hydrophobic coating regulated by bionic microstructure on the surface of concrete without disulfide segments and a preparation method thereof, comprising the following steps:

[0066] Preparation of polyaniline particles: 1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol and ultrasonicated for 10min. 5mmol aniline was dissolved in the above solution, mixed evenly, and 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanically stirred for 5min, and allowed to stand for 4h. The obtained solution was centrifuged at 8000r / min for 10min with aqueous solution, and the sediment was obtained and dried at 80℃ for 8h to obtain superhydrophobic sea urchin-like polyaniline particles.

[0067] Preparation of silicone resin: 3.37mmol isophorone diisocyanate was dissolved in 10ml butyl acetate and placed in a three-necked flask. 1mmol amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml butyl acetate and added to the above isocyanate solution at a speed of 0.5r / min through a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer (PDF). The infrared characterization of the resin synthesis is shown in Figure 2, which proves that the silicone resin without disulfide segments was successfully prepared. The reaction temperature was raised to 80°C, 2mmol fluorinated benzidine was dissolved in 20ml butyl acetate, and the above prepolymer solution was added. The reaction was reacted for 4h in the presence of 0.5% dibutyltin dilaurate by mass fraction to obtain a multi-reversible functional bond silicone resin.

[0068] Preparation of highly durable super-hydrophobic coating regulated by bionic microstructure: functionalized organic silicone resin solution is spin-coated on the surface of concrete substrate for pre-curing treatment; functional sea urchin super-hydrophobic particles are dispersed in organic solvent under ultrasonic conditions to prepare polyaniline dispersion, and then the particle dispersion is sprayed on the surface of concrete substrate treated with resin pre-curing using a spray gun. The obtained coating is dried at room temperature 50°C for 3h, and a highly durable bionic super-hydrophobic composite coating can be obtained without disulfide-segmented silicon-based resin.

[0069] Comparative Example 1

[0070] Comparative Example 1 of the present invention provides a hydrophobic coating on a concrete surface without polyaniline and a preparation method thereof, comprising the following steps:

[0071] Preparation of silicone resin: 3.37mmol isophorone diisocyanate was dissolved in 10ml butyl acetate and placed in a three-necked flask. 1mmol amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml butyl acetate and added to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer. The reaction temperature was raised to 80°C, 1mmol disulfide segment and 1mmol fluorinated benzidine were dissolved in 20ml butyl acetate, and the above prepolymer solution was added. The reaction was reacted for 4h in the presence of 0.5% dibutyltin dilaurate by mass fraction to obtain a silicone resin.

[0072] Preparation of coating: The organic silicone resin solution was spin-coated on the surface of the concrete substrate, and the obtained coating was dried at room temperature 50°C for 3 hours to obtain a hydrophobic coating on the concrete surface without polyaniline. The surface water contact angle is as follows Figure 4 (a) shows 94 ± 3°. Without polyaniline, a highly durable biomimetic superhydrophobic composite coating cannot be obtained.

[0073] Comparative Example 2

[0074] Comparative Example 2 of the present invention provides a concrete surface hydrophobic coating and a preparation method thereof, comprising the following steps: (polyaniline particle concentration is 0.25 g / ml)

[0075] Preparation of polyaniline particles: 1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol and ultrasonicated for 10min. 5mmol aniline was dissolved in the above solution, mixed evenly, and then 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanically stirred for 5min, and allowed to stand for 4h. The obtained solution was centrifuged at 8000r / min for 10min with aqueous solution, and the sediment was obtained and dried at 80℃ for 8h to obtain polyaniline particles.

[0076] Preparation of silicone resin: 3.37mmol isophorone diisocyanate was dissolved in 10ml butyl acetate and placed in a three-necked flask. 1mmol amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml butyl acetate and added to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer. The reaction temperature was raised to 80°C, 1mmol disulfide segment and 1mmol fluorinated benzidine were dissolved in 20ml butyl acetate, and the above prepolymer solution was added. The reaction was reacted for 4h in the presence of 0.5% dibutyltin dilaurate by mass fraction to obtain a silicone resin.

[0077] Preparation of coating: spin-coat the organic silicone resin solution onto the surface of the concrete substrate for pre-curing treatment; take 2 ml of 0.25 g / ml functional sea urchin super-hydrophobic particles and disperse them in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then use a spray gun to spray the particle dispersion onto the surface of the concrete substrate treated with the resin pre-curing treatment. The obtained coating was dried at room temperature 50°C for 3 hours to obtain a composite coating. Its surface water contact angle is as follows: Figure 4 (b) shows 126±3°. When the polyaniline content is 0.25 g / ml, a highly durable biomimetic superhydrophobic composite coating cannot be obtained.

[0078] Comparative Example 3

[0079] Comparative Example 3 of the present invention provides a hydrophobic coating on a concrete surface and a preparation method thereof, comprising the following steps: (polyaniline particle concentration is 0.5 g / ml)

[0080] Preparation of polyaniline particles: 1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol and ultrasonicated for 10min. 5mmol aniline was dissolved in the above solution, mixed evenly, and then 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanically stirred for 5min, and allowed to stand for 4h. The obtained solution was centrifuged at 8000r / min for 10min with aqueous solution, and the sediment was obtained and dried at 80℃ for 8h to obtain polyaniline particles.

[0081] Preparation of silicone resin: 3.37mmol isophorone diisocyanate was dissolved in 10ml butyl acetate and placed in a three-necked flask. 1mmol amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml butyl acetate and added to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer. The reaction temperature was raised to 80°C, 1mmol disulfide segment and 1mmol fluorinated benzidine were dissolved in 20ml butyl acetate, and the above prepolymer solution was added. The reaction was reacted for 4h in the presence of 0.5% dibutyltin dilaurate by mass fraction to obtain a silicone resin.

[0082] Preparation of coating: spin-coat the organic silicone resin solution onto the surface of the concrete substrate for pre-curing treatment; take 2 ml of 0.5 g / ml functional sea urchin super-hydrophobic particles and disperse them in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then use a spray gun to spray the particle dispersion onto the surface of the concrete substrate treated with the resin pre-curing treatment. The obtained coating was dried at room temperature 50°C for 3 hours to obtain a composite coating. Its surface water contact angle is as follows: Figure 4 (c) shows 144±3°. When the polyaniline content is 0.5 g / ml, a highly durable biomimetic superhydrophobic composite coating cannot be obtained.

[0083] Example 6

[0084] Example 6 of the present invention provides a highly durable super-hydrophobic coating regulated by a bionic microstructure on a concrete surface and a preparation method thereof, comprising the following steps: (polyaniline particle concentration is 0.75 g / ml)

[0085] Preparation of polyaniline particles: 1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol and ultrasonicated for 10min. 5mmol aniline was dissolved in the above solution, mixed evenly, and 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanically stirred for 5min, and allowed to stand for 4h. The obtained solution was centrifuged at 8000r / min for 10min with aqueous solution, and the sediment was obtained and dried at 80℃ for 8h to obtain superhydrophobic sea urchin-like polyaniline particles.

[0086] Preparation of silicone resin: 3.37mmol isophorone diisocyanate was dissolved in 10ml butyl acetate and placed in a three-necked flask. 1mmol amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml butyl acetate and added to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer. The reaction temperature was raised to 80°C, 1mmol disulfide segment and 1mmol fluorinated benzidine were dissolved in 20ml butyl acetate, and the above prepolymer solution was added. The reaction was reacted for 4h in the presence of 0.5% dibutyltin dilaurate by mass fraction to obtain a multi-reversible functional bond silicone resin.

[0087] Preparation of highly durable super-hydrophobic coating regulated by bionic microstructure: Take the functionalized silicone resin solution and spin-coat it on the surface of the concrete substrate for pre-curing treatment; take 2 ml of functional sea urchin super-hydrophobic particles with a concentration of 0.75 g / ml, and disperse them in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then use a spray gun to spray the particle dispersion on the surface of the concrete substrate treated with resin pre-curing. The obtained coating was dried at room temperature 50°C for 3 hours to obtain a highly durable bionic super-hydrophobic composite coating. Its surface water contact angle is as follows Figure 4 (d) shows 152±3°. When the polyaniline content is 0.75 g / ml, a highly durable biomimetic superhydrophobic composite coating cannot be obtained.

[0088] Example 7

[0089] Example 7 of the present invention provides a highly durable super-hydrophobic coating regulated by a bionic microstructure on a concrete surface and a preparation method thereof, comprising the following steps: (polyaniline particle concentration is 1 g / ml)

[0090] Preparation of polyaniline particles: 1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol and ultrasonicated for 10min. 5mmol aniline was dissolved in the above solution, mixed evenly, and 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanically stirred for 5min, and allowed to stand for 4h. The obtained solution was centrifuged at 8000r / min for 10min with aqueous solution, and the sediment was obtained and dried at 80℃ for 8h to obtain superhydrophobic sea urchin-like polyaniline particles.

[0091] Preparation of silicone resin: 3.37mmol isophorone diisocyanate was dissolved in 10ml butyl acetate and placed in a three-necked flask. 1mmol amino-terminated polydimethylsiloxane (5000g / mol) was dissolved in 15ml butyl acetate and added to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer. The reaction temperature was raised to 80°C, 1mmol disulfide segment and 1mmol fluorinated benzidine were dissolved in 20ml butyl acetate, and the above prepolymer solution was added. The reaction was reacted for 4h in the presence of 0.5% dibutyltin dilaurate by mass fraction to obtain a multi-reversible functional bond silicone resin.

[0092] Preparation of highly durable super-hydrophobic coating regulated by bionic microstructure: Take the functionalized silicone resin solution and spin-coat it on the surface of the concrete substrate for pre-curing treatment; take 2 ml of functional sea urchin super-hydrophobic particles with a concentration of 1 g / ml, and disperse them in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then use a spray gun to spray the particle dispersion on the surface of the concrete substrate treated with resin pre-curing. The obtained coating was dried at room temperature 50°C for 3 hours to obtain a highly durable bionic super-hydrophobic composite coating. Its surface water contact angle is as follows Figure 4 (e) shows 155±3°. When the polyaniline content is 1 g / ml, a highly durable biomimetic super-hydrophobic composite coating is obtained.

[0093] The samples obtained in Example 7 were subjected to sandpaper polishing and tape sticking experiments to test their durability. The test results of the changes in the contact angle after 100 tape stickings and 800 sandpaper polishings are as follows: Figure 5 and 6 After multiple mechanical durability tests, the coating still maintains its surface superhydrophobic properties, proving its high mechanical durability.

[0094] Example 8

[0095] Example 8 of the present invention provides a highly durable super-hydrophobic coating regulated by a bionic microstructure on a concrete surface and a preparation method thereof, comprising the following steps: (polyaniline particle concentration is 1.25 g / ml)

[0096] Preparation of polyaniline particles: 1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol and ultrasonicated for 10min. 5mmol aniline was dissolved in the above solution, mixed evenly, and 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanically stirred for 5min, and allowed to stand for 8h. The obtained solution was centrifuged at 8000r / min for 10min with aqueous solution, and the sediment was obtained and dried at 80℃ for 4h to obtain superhydrophobic sea urchin polyaniline particles.

[0097] Preparation of silicone resin: 3.37mmol isophorone diisocyanate was dissolved in 10ml butyl acetate and placed in a three-necked flask. 1mmol amino-terminated polydimethylsiloxane (3000g / mol) was dissolved in 15ml butyl acetate and added to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump. The reaction was stirred at room temperature for 4h to obtain a silicone prepolymer. The reaction temperature was raised to 80°C, 1mmol disulfide segment and 1mmol fluorinated benzidine were dissolved in 20ml butyl acetate, and the above prepolymer solution was added. The reaction was reacted for 4h in the presence of 0.5% dibutyltin dilaurate by mass fraction to obtain a multi-reversible functional bond silicone resin.

[0098] Preparation of highly durable super-hydrophobic coating regulated by bionic microstructure: Take the functionalized silicone resin solution and spin-coat it on the surface of the concrete substrate for pre-curing treatment; take 2 ml of functional sea urchin super-hydrophobic particles with a concentration of 1.25 g / ml, and disperse them in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then use a spray gun to spray the particle dispersion on the surface of the concrete substrate treated with resin pre-curing. The obtained coating was dried at room temperature 50°C for 3 hours to obtain a highly durable bionic super-hydrophobic composite coating. Its surface water contact angle is as follows Figure 4 (f) shows 158±3°. When the polyaniline content is 1.25 g / ml, a highly durable biomimetic superhydrophobic composite coating is obtained.

[0099] Example 9

[0100] Embodiment 9 of the present invention provides a highly durable super-hydrophobic coating regulated by bionic microstructure on a concrete surface and a preparation method thereof, comprising the following steps:

[0101] Preparation of polyaniline particles: 1 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol and ultrasonicated for 10 min. 5 mmol of polyaniline was dissolved in the above solution, mixed evenly, and then 1 mmol of ammonium persulfate aqueous solution (6 ml) was added, mechanically stirred for 5 min, and allowed to stand for 4 h. The resulting solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the sediment was obtained and dried at 80°C for 8 h to obtain superhydrophobic sea urchin-like polyaniline particles.

[0102] Preparation of silicone resin with multiple reversible functional bonds: 3.37mmol of isophorone diisocyanate was dissolved in 10ml of butyl acetate and placed in a three-necked flask. 1mmol of amino-terminated polydimethylsiloxane (2500g / mol) was dissolved in 15ml of butyl acetate and added dropwise to the above isocyanate solution at a speed of 0.5r / min by a peristaltic pump, and stirred at room temperature for 4h to obtain a silicone prepolymer. The reaction temperature was raised to 80°C, 1mmol of disulfide segment and 1mmol of fluorinated benzidine were dissolved in 20ml of butyl acetate, and the above prepolymer solution was added, and the reaction was carried out for 4h in the presence of 0.5% dibutyltin dilaurate by mass fraction to obtain a silicone resin with multiple reversible functional bonds.

[0103] Preparation of highly durable super-hydrophobic coating regulated by bionic microstructure: take a functionalized silicone resin solution and spin-coat it on the surface of a concrete substrate for pre-curing treatment; functional sea urchin super-hydrophobic particles are dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then a spray gun is used to spray the particle dispersion on the surface of the concrete substrate that has been pre-cured with the resin. The resulting coating is dried at room temperature 50°C for 3 hours. When the molecular weight of polydimethylsiloxane is 2500 g / mol, a highly durable bionic super-hydrophobic composite coating can be obtained.

Claims

1. A surface coating, characterized in that: The invention comprises a polyaniline particle surface layer and an organic silicon resin base layer, wherein the mass ratio of the polyaniline particles to the organic silicon resin is 1 to 1.5:

2.

2. A method for preparing the surface coating according to claim 1, characterized in that: The method comprises the following steps: applying a polyaniline particle dispersion to the surface of a pre-cured silicone resin, and obtaining a surface coating after drying.

3. The method for preparing the surface coating according to claim 2, characterized in that: The specific preparation method is to apply a silicone resin solution to the surface of a substrate and perform a pre-curing treatment; polyaniline particles are dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline particle dispersion, and then the polyaniline particle dispersion is applied to the surface of the substrate after the resin pre-curing treatment, and a surface coating is obtained after drying.

4. The method for preparing the surface coating according to claim 2, characterized in that: The preparation method of the polyaniline particles is as follows: p-toluenesulfonic acid and aniline are weighed and dissolved in ethanol, and ultrasonically dispersed; ammonium persulfate is dissolved in pure water and mixed with the solution, stirred and then allowed to stand, and dried to obtain the polyaniline particles.

5. The method for preparing the surface coating according to claim 4, characterized in that: The molar ratio of p-toluenesulfonic acid, ammonium persulfate and aniline is 0.9-1.1:0.9-1.1:4.5-5.5, and the volume ratio of ethanol to pure water is 3.5-4.5:5.5-6.

5.

6. The method for preparing a surface coating according to claim 2, characterized in that: The preparation method of the organic silicone resin is as follows: adding an isocyanate solution dropwise to a polydimethylsiloxane solution, stirring and reacting at room temperature; heating to 70 to 90° C. after stirring for 4 to 6 hours, and adding a solution A to obtain the organic silicone resin under a catalytic reaction, wherein the solution A includes at least one of a disulfide segment and a fluorinated benzidine.

7. The method for preparing the surface coating according to claim 6, characterized in that: The molar ratio of the isocyanate to polydimethylsiloxane is 3:1-3.4:1, the molar ratio of the disulfide segment to polydimethylsiloxane is 0.9-1.2:1, and the molar ratio of the fluorinated benzidine to polydimethylsiloxane is 0.9-1.2:

1.

8. The method for preparing a surface coating according to claim 2, characterized in that: Methods of applying the silicone resin solution to the substrate include direct pouring, dripping, knife coating, brushing or spraying.

9. The method for preparing a surface coating according to claim 2, characterized in that: The pre-curing temperature is 40-80° C., and the pre-curing time is 10-30 minutes.

10. Use of the surface coating according to claim 1 or the surface coating prepared by any preparation method of claims 2 to 9 on various substrates, wherein the substrates include concrete, wood, glass and stainless steel plates.

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