A surface coating and method of making and use thereof

Abstract

The application discloses a surface coating and a preparation method and application thereof, and belongs to the field of surface coating technology. The surface coating comprises a polyaniline particle surface layer and an organic silicon resin base layer. The preparation method comprises the following steps: applying a polyaniline particle dispersion liquid to a pre-solidified organic silicon resin surface, and drying to obtain the surface coating. In the application, 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 maintain the adhesion to the base material and the micro-nano structure of the coating under the action of external force, high durability is realized, and the application prospect in the fields of base material self-cleaning and anti-icing is good.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coating, and particularly relates to a surface coating and a preparation method and application thereof. BACKGROUND

[0002] Common substrates such as concrete, wood and the like are easily damaged by factors such as freeze-thaw, water penetration, ion erosion and the like under natural environment, ultimately reducing the service life thereof. In view of this, the super-hydrophobic coating protection of such substrates under special environment is becoming a major research hotspot. As a kind of physical shielding, the super-hydrophobic coating protection can effectively inhibit the penetration of erosion materials, improve the durability of the coating, reduce the long-term maintenance cost of the substrate, and delay the damage of the substrate to a certain extent.

[0003] Bionic super-hydrophobic surface has attracted wide attention in the research of substrate surface protection due to its excellent water-repellent ability (water contact angle > 150°, rolling angle < 10°), and has rapidly developed in the fields of self-cleaning, anti-icing, freeze-thaw and corrosion protection. For the super-hydrophobic surface, low surface energy material and micro-nano rough structure are two indispensable prerequisites, so the current main method for preparing bionic super-hydrophobic surface is still to combine low surface energy "adhesive" with "hydrophobic particles". The combination of traditional adhesive and hydrophobic particles often faces two problems: on the one hand, the adhesive has poor adhesion with the substrate due to its low surface energy requirement, so that the material may be peeled off when subjected to external influences such as mechanical or chemical wear; on the other hand, there are incompatibility problems between the low surface energy adhesive material and the hydrophobic particles during the compounding process, and the layered and abrasion phenomena are easy to occur after long-term physical and chemical damage, ultimately leading to the disappearance of the super-hydrophobic properties of the composite coating and the failure of the durability. SUMMARY

[0004] The purpose of the present application is to provide a high-durability super-hydrophobic surface coating with high compatibility of resin particles and bionic microstructure control; and another purpose of the present application is to provide a preparation method and application of the surface coating.

[0005] The surface coating comprises a polyaniline particle surface layer and a silicone resin substrate layer, and the mass ratio of the polyaniline particles to the silicone resin is 1-1.5:2.

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

[0007] The preparation method of the surface coating comprises the following steps: applying a polyaniline particle dispersion liquid to the surface of a pre-solidified silicone resin, and drying to obtain a surface coating.

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

[0009] Preferably, the preparation method of the polyaniline particles is to dissolve p-toluenesulfonic acid and aniline in ethanol, and perform ultrasonic dispersion; ammonium persulfate is dissolved in pure water and mixed with the above solution, stirred and then left to stand, and dried to obtain 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 the ethanol to pure water is 3.5-4.5:5.5-6.5.

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

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

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

[0014] Preferably, the ultrasonic dispersion time is 8-10 min, the stirring time is 5-10 min, the stirring reaction temperature is 20-25℃, and the stirring reaction time is 4-6 h.

[0015] Preferably, the drying method of the polyaniline particles is to dry in an oven at 60-80℃ for 8-12 h.

[0016] Preferably, the preparation method of the organic silicon resin is to drop an isocyanate solution into a polydimethylsiloxane solution, and perform stirring reaction at room temperature; after stirring for 4-6 h, the temperature is increased to 70-90℃, and an A solution is added to obtain the organic silicon resin under catalytic reaction, wherein the A includes at least one of a disulfide segment and a fluorine-containing aniline.

[0017] Preferably, the preparation method of the organic silicon resin is to drop an isocyanate solution into a polydimethylsiloxane solution, and perform stirring reaction at room temperature; after stirring for 4-6 h, the temperature is increased to 70-90℃, and a mixed solution of a disulfide segment and a fluorine-containing aniline is added to obtain the organic silicon resin under catalytic reaction.

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

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

[0020] Preferably, the polydimethylsiloxane has a molecular weight of 2500 to 5000 g / mol.

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

[0022] Preferably, the solvents of the isocyanate solution and the A solution are butyl acetate.

[0023] Preferably, the mass fraction of the polydimethylsiloxane solution is 30 to 40%, and the mass fraction of each of the isocyanate, the disulfide segment, and the fluoroaniline in the butyl acetate solution is 10 to 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 the mass fraction in the mixed butyl acetate solution is 0.5 to 1%.

[0027] Preferably, the method of applying the silicone resin solution to the substrate includes directly pouring, drop coating, blade coating, brush coating, or spraying.

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

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

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

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

[0032] The surface coating described in the present application is applied to various substrates, including concrete, wood, glass, and stainless steel plates.

[0033] Advantages: Compared with the prior art, the present application has the following remarkable advantages:

[0034] (1) The present application prepares a high-durability super-hydrophobic composite coating on the surface of a substrate, which is obtained by using a bottom layer of pre-solidified multi-reversible bond organic silicon resin coating and a surface of sprayed biomimetic urchin-shaped polyaniline particles. The multi-hydrogen bond between the organic silicon resin and the surface of the substrate achieves high adhesion of the substrate, and the multi-hydrogen bond and π-π stacking between the urchin-shaped nanoparticles and the resin improve the overall compatibility of the composite coating, realizing strong mechanical anchoring of the particles-resin. This makes it still able to maintain adhesion to the substrate and the micro-nano structure of the coating under external force, realizing high durability.

[0035] (2) By preferentially selecting the material ratio and controlling the above process, the biomimetic microstructure-regulated composite coating prepared by the present application exhibits excellent super-hydrophobic performance. It has the ability to repel various liquid droplets such as orange juice, milk and coffee, and can remove surface silt stains under water flow, having good self-cleaning ability.

[0036] (3) The super-hydrophobic composite coating prepared by the present application can resist a series of chemical and physical durability tests, and the high durability of the composite coating is verified by methods such as sandpaper abrasion (abrasion resistance distance of the coating under 1000 mesh sandpaper with a load of 100g) and adhesive tape pasting. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 is a schematic diagram of the micro-morphology of polyaniline in Example 1 of the present application;

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

[0039] Figure 3 is a schematic diagram of the preparation of the composite coating in Example 1 of the present application; 1-organic silicon resin layer, 2-polyaniline particles;

[0040] Figure 4 is a schematic diagram of the surface hydrophobic angle under different polyaniline spraying concentrations in Examples 6-8 and Comparative Examples 2-3 of the present application;

[0041] Figure 5 is a schematic diagram of the effect of sandpaper polishing times on the contact angle of the composite coating in Example 7 of the present application;

[0042] Figure 6 is a schematic diagram of the effect of adhesive tape pasting times on the contact angle of the composite coating in Example 7 of the present application. DETAILED DESCRIPTION

[0043] The technical solutions of the present application will be further described below in combination with examples and drawings.

[0044] Example 1

[0045] Example 1 of the present application provides a high durability superhydrophobic coating with biomimetic microstructure regulated on concrete surface and a preparation method thereof, comprising the following steps:

[0046] Preparation of polyaniline particles: 1 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol, and ultrasonic broken instrument was used for ultrasonic treatment for 10 min. 5 mmol of aniline was dissolved in the above solution, and after being uniformly mixed, 1 mmol of ammonium persulfate aqueous solution (6 ml) was added, mechanical stirring was carried out for 5 min, and standing was carried out for 4 h. The obtained solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the subsidence was obtained, and the superhydrophobic sea urchin-like polyaniline particles were obtained by drying at 80℃ for 8 h. The micro-morphology of the sea urchin-like polyaniline particles is shown in Figure 1 The surface of the obtained polyaniline presents a thorn-like sea urchin morphology, and the water contact angle of the surface is 153.8±1°, realizing superhydrophobicity.

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

[0048] Preparation of high durability superhydrophobic coating with biomimetic microstructure regulated: the functionalized silicone resin solution was spin-coated onto the surface of the concrete substrate, and pre-curing treatment was carried out; the polyaniline particles were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion liquid, and then the particle dispersion liquid was sprayed onto the surface of the resin pre-cured concrete substrate by using an airbrush. The obtained coating was dried at room temperature for 3 h, and when the molecular weight of the polydimethylsiloxane was 5000 g / mol, a high durability biomimetic superhydrophobic composite coating could be obtained.

[0049] Example 2

[0050] Example 2 of the present application provides a high durability superhydrophobic coating with biomimetic microstructure regulated on concrete surface and a preparation method thereof, comprising the following steps:

[0051] Preparation of polyaniline particles: 0.9 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol, and was ultrasonically broken by an ultrasonic crusher for 10 min. 4.5 mmol of aniline was dissolved in the above solution, and after being mixed uniformly, 0.9 mmol of ammonium persulfate aqueous solution (6 ml) was added, and was mechanically stirred for 5 min, and was left to stand for 4 h. The obtained solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the sinking matter was obtained, and was dried at 60°C for 8 h to obtain superhydrophobic urchin-like polyaniline particles.

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

[0053] Preparation of a high-durability superhydrophobic coating regulated by biomimetic microstructure: the functionalized silicone resin solution was spin-coated onto the surface of a concrete substrate, and was subjected to a pre-curing treatment; the polyaniline particles were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion liquid, and then the particle dispersion liquid was sprayed onto the surface of the resin pre-curing treated concrete substrate using a spray gun. The obtained coating was dried at room temperature for 3 h at 50°C to obtain a high-durability biomimetic superhydrophobic composite coating.

[0054] Example 3

[0055] Example 3 of the present application provides a high-durability superhydrophobic coating regulated by biomimetic microstructure on a concrete surface and a preparation method thereof, which comprises the following steps:

[0056] Preparation of polyaniline particles: 0.9 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol, and was ultrasonically broken by an ultrasonic crusher for 10 min. 4.5 mmol of aniline was dissolved in the above solution, and after being mixed uniformly, 0.9 mmol of ammonium persulfate aqueous solution (6 ml) was added, and was mechanically stirred for 5 min, and was left to stand for 4 h. The obtained solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the sinking matter was obtained, and was dried at 60°C for 8 h to obtain superhydrophobic urchin-like polyaniline particles.

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

[0058] Preparation of a high-durability superhydrophobic coating with biomimetic microstructure regulation: The functionalized silicone resin solution was spin-coated onto the surface of a concrete substrate and subjected to a pre-curing treatment. Polyaniline particles were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then the particle dispersion was sprayed onto the surface of the resin pre-cured concrete substrate using a spray gun. The resulting coating was dried at room temperature for 3 h at 50℃ to obtain a high-durability biomimetic superhydrophobic composite coating.

[0059] Example 4

[0060] Example 4 of the present application provides a high-durability superhydrophobic coating with biomimetic microstructure regulation on a fluorine-free segment-containing concrete surface and a preparation method thereof, comprising the following steps:

[0061] Preparation of polyaniline particles: 1 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol and subjected to ultrasonic crushing for 10 min. 5 mmol of aniline was dissolved in the above solution, and after being mixed uniformly, 1 mmol of ammonium persulfate aqueous solution (6 ml) was added, mechanically stirred for 5 min, and left standing for 4 h. The resulting solution was centrifuged with an aqueous solution at 8000 r / min for 10 min to obtain the precipitate, which was dried at 80℃ for 8 h to obtain superhydrophobic sea urchin-like polyaniline particles.

[0062] Preparation of silicone resin: 3.4 mmol of isophorone diisocyanate was dissolved in 10 ml of butyl acetate and placed in a three-necked flask. 1 mmol of amino-terminated polydimethylsiloxane (5000 g / mol) was dissolved in 15 ml of butyl acetate and added dropwise to the above isocyanate solution at a rate of 0.5 r / min by using a peristaltic pump. The reaction was stirred at room temperature for 4 h to obtain a silicone prepolymer (PDS). The infrared characterization of the resin synthesis is shown in Figure 2 Preparation of silicone resin: 3.4 mmol of isophorone diisocyanate was dissolved in 10 ml of butyl acetate and placed in a three-necked flask. 1 mmol of amino-terminated polydimethylsiloxane (5000 g / mol) was dissolved in 15 ml of butyl acetate and added dropwise to the above isocyanate solution at a rate of 0.5 r / min by using a peristaltic pump. The reaction was stirred at room temperature for 4 h to obtain a silicone prepolymer (PDS). The infrared characterization of the resin synthesis is shown in

[0063] Preparation of high durability biomimetic microstructure regulated superhydrophobic composite coating: functionalized silicone resin solution was spin-coated onto the surface of a concrete substrate, and pre-cured; functional sea urchin superhydrophobic particles were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then the particle dispersion was sprayed onto the resin pre-cured concrete substrate surface using a spray gun. The resulting coating was dried at 50°C for 3h, and a high durability biomimetic superhydrophobic composite coating was obtained without fluorine-containing segment silicone-based resin.

[0064] Example 5

[0065] Example 5 of the present application provides a high durability biomimetic microstructure regulated superhydrophobic coating without disulfide segment on the surface of concrete and a preparation method thereof, comprising the following steps:

[0066] Preparation of polyaniline particles: 1mmol p-toluenesulfonic acid was dissolved in 4ml ethanol, and ultrasonic broken instrument was used for ultrasonic treatment for 10min. 5mmol aniline was dissolved in the above solution, and after mixing uniformly, 1mmol ammonium persulfate aqueous solution (6ml) was added, mechanical stirring was carried out for 5min, and standing was carried out for 4h. The obtained solution was centrifuged with water solution at 8000r / min for 10min, and the subsidence was obtained, and the superhydrophobic sea urchin-like polyaniline particles were obtained by drying at 80°C for 8h.

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

[0068] Preparation of high durability biomimetic microstructure regulated superhydrophobic coating: functionalized silicone resin solution was spin-coated onto the surface of a concrete substrate, and pre-cured; functional sea urchin superhydrophobic particles were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then the particle dispersion was sprayed onto the resin pre-cured concrete substrate surface using a spray gun. The resulting coating was dried at 50°C for 3h, and a high durability biomimetic superhydrophobic composite coating was obtained without disulfide segment silicone-based resin.

[0069] Comparative Example 1

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

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

[0072] Coating preparation: The silicone resin solution was spin-coated onto the surface of a concrete substrate, and the resulting coating was dried at room temperature for 3 h at 50°C to obtain a concrete surface hydrophobic coating without polyaniline. The surface water contact angle thereof was 94±3° as shown in (a). A high-durability biomimetic superhydrophobic composite coating cannot be obtained without polyaniline. Figure 4 (a) shown. A high-durability biomimetic superhydrophobic composite coating cannot be obtained without polyaniline.

[0073] Comparative Example 2

[0074] Comparative Example 2 of the present application provides a concrete surface hydrophobic coating and a method for preparing the same, comprising the following steps: (the concentration of polyaniline particles is 0.25 g / ml)

[0075] Preparation of polyaniline particles: 1 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol, and ultrasonically broken by an ultrasonic crusher for 10 min. 5 mmol of aniline was dissolved in the above solution, and after being mixed uniformly, 1 mmol of ammonium persulfate aqueous solution (6 ml) was added, mechanically stirred for 5 min, and left to stand for 4 h. The resulting solution was centrifuged with an aqueous solution at 8000 r / min for 10 min, and the precipitate was obtained, which was dried at 80°C for 8 h to obtain polyaniline particles.

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

[0077] Coating preparation: The silicone resin solution was spin-coated onto the surface of the concrete substrate and pre-cured; 2 ml of functional sea urchin super-hydrophobic particles with a concentration of 0.25 g / ml were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then the particle dispersion was sprayed onto the surface of the resin pre-cured concrete substrate using a spray gun. The resulting coating was dried at room temperature for 3 h at 50 °C to obtain a composite coating. The surface water contact angle of the coating was 126±3°, as shown in Figure 4 (b). When the polyaniline content was 0.25 g / ml, a high-durability biomimetic super-hydrophobic composite coating could not be obtained.

[0078] Comparative Example 3

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

[0080] Preparation of polyaniline particles: 1 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol, and ultrasonic fragmentation was performed for 10 min. 5 mmol of aniline was dissolved in the above solution, and after uniform mixing, 1 mmol of ammonium persulfate aqueous solution (6 ml) was added, mechanical stirring was performed for 5 min, and standing was performed for 4 h. The resulting solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the precipitate was obtained, and the polyaniline particles were obtained by drying at 80 °C for 8 h.

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

[0082] Coating preparation: The silicone resin solution was spin-coated onto the surface of the concrete substrate and pre-cured; 2 ml of functional sea urchin super-hydrophobic particles with a concentration of 0.25 g / ml were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then the particle dispersion was sprayed onto the surface of the resin pre-cured concrete substrate using a spray gun. The resulting coating was dried at room temperature for 3 h at 50 °C to obtain a composite coating. The surface water contact angle of the coating was 126±3°, as shown in Figure 4 (c). When the polyaniline content was 0.5 g / ml, a high-durability biomimetic super-hydrophobic composite coating could not be obtained.

[0083] Example 6

[0084] Embodiment 6 of the present application provides a high durability biomimetic microstructure regulated superhydrophobic coating on concrete surface and a preparation method thereof, comprising the following steps: (polyaniline particle concentration is 0.75 g / ml)

[0085] Preparation of polyaniline particles: 1 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol, and ultrasonic broken instrument was used for ultrasonic treatment for 10 min. 5 mmol of aniline was dissolved in the above solution, and 1 mmol of ammonium persulfate aqueous solution (6 ml) was added after uniform mixing. Mechanical stirring was performed for 5 min, and then the solution was left to stand for 4 h. The obtained solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the precipitate was obtained. The precipitate was dried at 80℃ for 8 h to obtain superhydrophobic sea urchin-like polyaniline particles.

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

[0087] Preparation of biomimetic microstructure regulated high durability superhydrophobic coating: the functional silicone resin solution was spin-coated onto the surface of the concrete substrate, and a pre-curing treatment was performed. 2 ml of functional sea urchin superhydrophobic particles with a concentration of 0.75 g / ml were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then the particle dispersion was sprayed onto the resin pre-cured concrete substrate surface using a spray gun. The obtained coating was dried at room temperature for 3 h, and a high durability biomimetic superhydrophobic composite coating was obtained. The surface water contact angle of the coating was 152±3° as shown in (d). Figure 4 (d) showed that the surface water contact angle was 152±3°. When the polyaniline content was 0.75 g / ml, a high durability biomimetic superhydrophobic composite coating could not be obtained.

[0088] Embodiment 7

[0089] Embodiment 7 of the present application provides a high durability biomimetic microstructure regulated superhydrophobic coating on concrete surface and a preparation method thereof, comprising the following steps: (polyaniline particle concentration is 1 g / ml)

[0090] Preparation of polyaniline particles: 1 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol and broken up by ultrasonic instrument for 10 min. 5 mmol of aniline was dissolved in the above solution, and after being mixed uniformly, 1 mmol of ammonium persulfate aqueous solution (6 ml) was added, mechanical stirring was carried out for 5 min, and standing was carried out for 4 h. The obtained solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the subsidence was obtained, and the superhydrophobic sea urchin-like polyaniline particles were obtained by drying at 80℃ for 8 h.

[0091] Preparation of silicone resin: 3.37 mmol of isophorone diisocyanate was dissolved in 10 ml of butyl acetate and placed in a three-necked flask. 1 mmol of amino-terminated polydimethylsiloxane (5000 g / mol) was dissolved in 15 ml of butyl acetate, and was added dropwise to the above isocyanate solution at a speed of 0.5 r / min by peristaltic pump, and stirring reaction was carried out at room temperature for 4 h to obtain a silicone prepolymer. The reaction was warmed to 80℃, 1 mmol of dithio segment and 1 mmol of fluorine-containing diazosine were dissolved in 20 ml of butyl acetate, and were added to the above prepolymer solution, and reaction was carried out in the presence of 0.5% (mass fraction) dibutyltin dilaurate for 4 h to obtain a silicone resin with multiple reversible functional bonds.

[0092] Preparation of a high-durability superhydrophobic coating with biomimetic microstructure regulation: the functional silicone resin solution was spin-coated onto the surface of a concrete substrate for pre-curing treatment; 2 ml of functional sea urchin superhydrophobic particles with a concentration of 1 g / ml were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then the particle dispersion was sprayed onto the surface of the resin pre-cured concrete substrate using a spray gun. The obtained coating was dried at room temperature for 3 h, and a high-durability biomimetic superhydrophobic composite coating was obtained. The surface water contact angle of the coating was 155±3° as shown in (e). Figure 4 (e) and a polyaniline content of 1 g / ml.

[0093] The sample obtained in Example 7 was subjected to sandpaper polishing and adhesive tape sticking experiments to test its durability, and the test results of the influence of 100 times of adhesive tape sticking and 800 times of sandpaper polishing on the contact angle are shown in (a) and (b). Figure 5 and 6 After undergoing multiple mechanical durability tests, the coating still maintained the surface superhydrophobic property, proving that it has high mechanical durability.

[0094] Example 8

[0095] Example 8 of the present application provides a high-durability superhydrophobic coating with biomimetic microstructure regulation on a concrete surface and a preparation method thereof, which comprises the following steps: (the concentration of polyaniline particles is 1.25 g / ml)

[0096] Polyaniline particle preparation: 1 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol, and was ultrasonically broken by an ultrasonic crusher for 10 min. 5 mmol of aniline was dissolved in the above solution, and 1 mmol of ammonium persulfate aqueous solution (6 ml) was added after mixing uniformly, and was mechanically stirred for 5 min, and was left to stand for 8 h. The obtained solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the sinking matter was obtained, and was dried at 80°C for 4 h to obtain superhydrophobic sea urchin-like polyaniline particles.

[0097] Silicone resin preparation: 3.37 mmol of isophorone diisocyanate was dissolved in 10 ml of butyl acetate, and was placed in a three-necked flask. 1 mmol of amino-terminated polydimethylsiloxane (3000 g / mol) was dissolved in 15 ml of butyl acetate, and was added dropwise to the above isocyanate solution at a rate of 0.5 r / min by a peristaltic pump, and was stirred at room temperature for 4 h to obtain a silicone prepolymer. The reaction was warmed to 80°C, 1 mmol of a dithio segment and 1 mmol of a fluorine-containing diazosulfonate were dissolved in 20 ml of butyl acetate, and were added to the above prepolymer solution, and were reacted for 4 h in the presence of 0.5% by mass of dibutyltin dilaurate to obtain a silicone resin having multiple reversible functional bonds.

[0098] Preparation of a high-durability superhydrophobic coating regulated by a biomimetic microstructure: The functionalized silicone resin solution was spin-coated onto the surface of a concrete substrate, and was subjected to a pre-curing treatment; 2 ml of functional sea urchin superhydrophobic particles having a concentration of 1.25 g / ml were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion liquid, and then the particle dispersion liquid was sprayed onto the surface of the resin pre-cured concrete substrate using a spray gun. The obtained coating was dried at room temperature for 3 h, and a high-durability biomimetic superhydrophobic composite coating was obtained. The surface water contact angle thereof was 158 ± 3° as shown in (f). Figure 4 (f) showed that it was 158 ± 3°. A high-durability biomimetic superhydrophobic composite coating was obtained when the polyaniline content was 1.25 g / ml.

[0099] Example 9

[0100] Example 9 of the present application provides a high-durability superhydrophobic coating regulated by a biomimetic microstructure on a concrete surface and a preparation method thereof, which comprises the following steps:

[0101] Polyaniline particle preparation: 1 mmol of p-toluenesulfonic acid was dissolved in 4 ml of ethanol, and was ultrasonically broken by an ultrasonic crusher for 10 min. 5 mmol of aniline was dissolved in the above solution, and 1 mmol of ammonium persulfate aqueous solution (6 ml) was added after mixing uniformly, and was mechanically stirred for 5 min, and was left to stand for 8 h. The obtained solution was centrifuged at 8000 r / min for 10 min with an aqueous solution, and the sinking matter was obtained, and was dried at 80°C for 4 h to obtain superhydrophobic sea urchin-like polyaniline particles.

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

[0103] Preparation of a high-durability biomimetic microstructure-regulated superhydrophobic coating: The functionalized silicone resin solution was spin-coated onto the surface of a concrete substrate and subjected to a pre-curing treatment. Functional sea urchin superhydrophobic particles were dispersed in an organic solvent under ultrasonic conditions to prepare a polyaniline dispersion, and then the particle dispersion was sprayed onto the surface of the resin pre-cured concrete substrate using a spray gun. The resulting coating was dried at room temperature for 3 h at 50°C, and a high-durability biomimetic superhydrophobic composite coating was obtained when the molecular weight of the polydimethylsiloxane was 2500 g / mol.

Claims

1. A surface coating, characterized in that, The surface coating comprises a polyaniline particle surface layer and a silicone resin base layer, the mass ratio of the polyaniline particle to the silicone resin is 1-1.5:2; the polyaniline particle has a sea urchin-like micro-nano structure; the silicone resin base layer is formed by reacting isocyanate, polydimethylsiloxane and A, the A being a fluorine-containing diazoline; the polyaniline particle is mechanically anchored in the base layer through π-π stacking and hydrogen bonding between the polyaniline particle and the silicone resin base.

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

3. The method of claim 2, wherein the surface coating is prepared by a process comprising: The specific preparation method comprises the following steps: applying a silicone resin solution to a substrate surface and performing a pre-curing treatment; dispersing polyaniline particles in an organic solvent under ultrasonic conditions to prepare a polyaniline particle dispersion liquid, and then applying the polyaniline particle dispersion liquid to the substrate surface after the resin pre-curing treatment, and drying to obtain a surface coating.

4. The method of claim 2, wherein the surface coating is prepared by a process comprising: The preparation method of the polyaniline particle comprises the following steps: dissolving p-toluenesulfonic acid and aniline in ethanol and ultrasonic dispersion; dissolving ammonium persulfate in pure water and mixing with the above solution, stirring and then standing, and drying to obtain polyaniline particles.

5. The method of claim 4, wherein the surface coating is prepared by a process comprising: 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 the ethanol to pure water is 3.5-4.5:5.5-6.

5.

6. The method of claim 2, wherein the surface coating is prepared by a process comprising: The preparation method of the silicone resin comprises the following steps: dropping an isocyanate solution into a polydimethylsiloxane solution, stirring and reacting at room temperature; after stirring for 4-6 h, heating to 70-90℃, and adding an A solution, catalytic reaction to obtain a silicone resin, the A being a fluorine-containing diazoline.

7. The method of claim 6, wherein the surface coating is prepared by, The molar ratio of the isocyanate to the polydimethylsiloxane is 3:1-3.4:1, and the molar ratio of the fluorine-containing diazoline to the polydimethylsiloxane is 0.9-1.2:

1.

8. The method of claim 2, wherein the surface coating is prepared by a process comprising: The method for applying the silicone resin solution to the substrate comprises direct pouring, drop coating, blade coating, brush coating or spraying.

9. The method of claim 2, wherein the surface coating is prepared by a process comprising: The pre-curing temperature is 40-80℃, and the pre-curing time is 10-30 min.

10. Use of the surface coating of claim 1 or the surface coating prepared by the preparation method of any one of claims 2-9 in various substrates, the substrates including concrete, wood, glass and stainless steel plate.

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