CN115181495B - A super-amphiphobic super-weather-resistant silicone protective coating and preparation method thereof - Google Patents

Abstract

The invention discloses a super-amphiphobic and super-weather-resistant organic silicon protective coating and a preparation method thereof. Particles, catalysts, silicone leveling agents, dispersants, silicone defoamers, and organic solvents. The organosilicon resin of the present invention is modified by the partial dealcoholization and condensation reaction of fluorocarbon alcohols, and introduces high-bond energy fluorocarbon segments, so that the resin matrix has an extremely low surface energy, while the surface of polydopamine biomimetic modified nanoparticles contains The highly active phenolic hydroxyl group can form stable covalent bonds with the modified silicone resin matrix and the surface of metal and concrete substrates, which not only significantly improves the weather resistance and hydrophobic and oleophobic properties of the protective coating, but also effectively improves the protective coating. , Bond strength of concrete base.

Description

A super-amphiphobic super-weather-resistant silicone protective coating and preparation method thereof

technical field

The invention belongs to the technical field of protective coatings, and relates to a super-amphiphobic and super-weather-resistant silicone protective coating and a preparation method thereof.

Background technique

In recent years, the construction of major projects has expanded to plateaus, oceans, mountains and other regions. Extreme environments (high ultraviolet rays, large temperature differences, high humidity, high salinity, freeze-thaw, etc.) pose a huge challenge to the project's century-old life, and also pose a challenge to protective materials. Higher, more demands. Superamphiphobic surfaces (contact angle to water and oil > 150°, rolling angle < 10°) have attracted extensive attention from researchers due to their excellent properties such as antifouling, self-cleaning, anti-icing, and anti-corrosion. Since water and oil will not infiltrate the surface of the super-amphiphobic protective coating, it can solve the problem that a single super-hydrophobic protective coating is easily polluted by external oily substances, so the coating is widely used in oil fields, oceans, transportation and industrial production and other fields have broader application prospects. However, since the surface energy of oily substances is much lower than that of water, this requires the protective coating to have a lower surface energy and a finer and more uniform micro-nano structure. Most of the existing super-hydrophobic or super-amphiphobic protective coatings have complex preparation processes, poor adhesion between the coating and the substrate, and are not wear-resistant and weather-resistant when used in extreme outdoor environments. Super-hydrophobic or super-amphiphobic properties do not have Long-acting, short lifespan.

Patent CN112375244A provides a wear-resistant self-cleaning super-amphiphobic coating and its preparation method. The operation steps are as follows: polystyrene microspheres are coated on a transparent substrate by pulling coating; and then coated by magnetron sputtering. A layer of metal film; followed by ultrasonic removal of polystyrene microspheres in a water bath to obtain a metal film with a grooved microstructure and a layer of metal oxide grown on its surface by anodic oxidation; then continue on this metal oxide Nanoparticles are grown; finally, they are modified with low surface energy to obtain a coating attached to a transparent substrate. Although the superamphiphobic coating prepared by this scheme has good wear resistance, the operation process is numerous and the preparation process is complicated. In addition, the low surface energy modification of the nanoparticles on the coating surface will be damaged after a period of service due to wear and oxidation degradation reactions. The super-amphiphobic effect is reduced, which directly affects the protective effect of the coating.

Patent CN112812676A provides a superamphiphobic acid-resistant coating and its preparation method. The operation steps are as follows: first, immerse the nano-SiO2 particles in the ethanol solution of fluorosilane to modify at room temperature, grind and disperse after drying to obtain the modified Nano-SiO2 particles; then the polyurethane anti-corrosion coating is coated on the surface of the pretreated substrate, dried, and after the coating on the surface of the substrate enters a semi-cured state, the modified nano-SiO2 particles are sprayed on the semi-cured The surface of the coating in the state is cured to obtain a super amphiphobic acid-resistant coating. This solution solves the problems of complex preparation process, expensive instruments and equipment, high preparation cost and harsh preparation conditions in the prior art. However, it is difficult to control the semi-cured state of the polyurethane coating during the preparation process of the coating. If the modified nano-SiO2 particles are sprayed too early, they are likely to completely sink into the polyurethane coating and cannot achieve the desired effect. If the spraying is too late, it is easy to cause modification. The bond between the nano-SiO2 particles and the coating is not firm and falls off. In addition, due to the poor aging resistance of polyurethane, the coating is prone to photooxidative degradation reaction due to ultraviolet light irradiation during outdoor use, the polymer decomposes, and the modified nano-SiO2 particles fall off from the coating surface to form powder.

Patent CN112940585A provides a method for preparing a self-cleaning amphobic coating for degrading NO. In the coating, nano-silica is introduced to avoid the direct degradation of epoxy resin by strong oxidizing groups produced by titanium dioxide nanotubes, thereby To improve the UV stability of the coating. However, the mass fraction of epoxy resin and curing agent in this scheme is 3-4 times that of fluorosilane, and the main resin of the whole coating is still epoxy resin. Although nano-silica can slow down the impact of titanium dioxide nanotubes on epoxy The strong oxidative degradation reaction of the resin, but the coating is inevitably exposed to ultraviolet light in the long-term outdoor service process, and the photo-oxidative degradation reaction occurs. The main epoxy resin is oxidatively degraded, and the nanoparticles are powdered and peeled off. The coating fails and seriously reduces its service life.

Contents of the invention

In order to overcome the shortcomings of the existing protective coatings such as short weather resistance, unsustainable super-amphiphobic effect, and low adhesion between the protective coating and the surface of the substrate or between nanoparticles and the coating, the present invention provides a super-amphiphobic The amphobic super-weather-resistant organic silicon protective coating and the preparation method thereof also solve the problems of complicated preparation process, harsh synthesis conditions and expensive instruments and equipment in the prior art.

The invention provides a super-amphiphobic and super-weather-resistant silicone protective coating, the raw material components and parts by weight of each component are as follows:

30-60 parts of silicone resin,

Fluorocarbon alcohol 20-30 parts,

15-25 parts of polydopamine biomimetic modified nanoparticles;

The silicone resin is trimethoxyl or triethoxysilane containing long-chain alkyl groups, wherein the number of carbon atoms in the long-chain alkyl groups is 6-18;

The fluorocarbon alcohol is a straight-chain fluorocarbon alcohol with 5-10 carbon atoms and no fluorine group on the carbon atom directly connected to the hydroxyl group;

The nanoparticles in the polydopamine biomimetic modified nanoparticles are fibrous rod-like or filamentary structures, selected from one or more of carbon nanotubes, carbon nanofibers, palygorskite, titanium dioxide whiskers, and potassium titanate whiskers. kind of mix.

The super-amphiphobic super-weather-resistant silicone protective coating, its raw material components and parts by weight of each component also include the following:

The catalyst is any one of naphthenates or carboxylates of Pb, Fe, Zn, Sn, Co, etc., phosphazene chloride and phthalate complexes.

Further preferably, the mass ratio of the silicone resin to the fluorocarbon alcohol is (1.5-2): 1, and the mass sum of the silicone resin, the fluorocarbon alcohol and the polydopamine biomimetic modified nanoparticles accounts for 65%- 85%.

Further preferably, the fluorocarbon alcohol is selected from 1H, 1H-nonafluoro-1-pentanol, 1H, 1H-undecafluoro-1-hexanol, 1H, 1H-tridecafluoro-1-heptanol, 1H, Any of 1H-pentadecafluoro-1-octanol, 1H,1H-heptadecafluoro-1-nonanol, and 1H,1H-nonadecafluoro-1-decanol.

The polydopamine biomimetic modified nanoparticles are prepared by oxidative self-polymerization of dopamine hydrochloride on the surface of the nanoparticles, and its preparation method is well known to those skilled in the art. The particle size of the nanoparticles is 25-100nm.

Further preferably, the catalyst is lead naphthenate, iron naphthenate, zinc naphthenate, tin naphthenate, cobalt naphthenate, dibutyltin dilaurate, stannous octoate, hexachlorocyclotriphosphazene, titanium Any of the ester complexes.

The organosilicon leveling agent, dispersant, and organosilicon defoamer described in the present invention are commonly used products related to silicone resin coatings in the field of this industry, and are widely known to those skilled in the art; preferably, the organosilicon leveling agent The dispersant can be selected from one or more of models such as BYK-325N, BYK-333, BYK-306 of commercially available BYK Chemical Company; preferably, the dispersant can be selected from BYK-110 of commercially available BYK Chemical Company , BYK-111, BYK-161, BYK-163 and other models; preferably, the silicone defoamer can be selected from commercially available BYK-088, BYK-085 of BYK Chemical Company, Dow Corning One or more of the AFE-0120, ACP-0544, 1430, DC-7 and other models.

The organic solvent described in the present invention is a mixture of one or more of toluene, xylene, cyclohexane, ethyl acetate, butyl acetate and butanol.

The present invention also provides a method for preparing a super-amphiphobic super-weather-resistant silicone protective coating, the specific steps of which are as follows:

(1) Preparation of modified silicone resin: Add silicone resin and fluorocarbon alcohol into a reaction vessel, stir and heat up to 60-80°C, and continue to react at this temperature for 1-2h to obtain modified silicone resin.

(2) Add the modified silicone resin, polydopamine biomimetic modified nanoparticles, catalyst, silicone leveling agent, dispersant, silicone defoamer and solvent into the paint mixing tank and stir at a high speed at room temperature After mixing evenly, a super-amphiphobic super-weather-resistant silicone protective coating is obtained.

(3) Spray the protective coating obtained in step (2) on the surface of the substrate after surface treatment, and cure and dry under normal temperature conditions to obtain a silicone protective coating with super-amphiphobic and super-weather resistance.

The advantages and beneficial effects that the present invention possesses compared with prior art are:

(a) The organosilicon resin of the present invention is a long-chain alkyl silicone resin, which itself has good hydrophobicity; secondly, a high-bond-energy fluorocarbon segment is introduced after modification of its partial dealcoholization and condensation reaction by fluorocarbon alcohols , so that the resin matrix has an extremely low surface energy, which significantly improves the weather resistance and hydrophobic and oleophobic properties of the protective coating.

(b) Polydopamine biomimetic modified nanoparticles On the one hand, the highly active phenolic hydroxyl groups on the surface can form stable covalent bonds with the modified silicone resin matrix and the surface of metal and concrete substrates, effectively improving the crosslinking degree of the resin matrix itself , so that the nanoparticles and the resin matrix are integrated; in addition, the bonding strength between the protective coating and the metal and concrete substrates is effectively improved, and the bonding strengths on the metal and concrete substrates exceed 10 MPa and 4MPa respectively; on the other hand, The introduction of polydopamine biomimetic modified nanoparticles with uniform particle size increases the fine roughness of the protective coating surface and further improves the super-amphiphobic effect of the protective coating. Through actual experiments, it is found that water, ethylene glycol, hexadecane, etc. The contact angles of the droplets on the surface of the protective coating of the present invention can respectively reach 165-170°, 158-165°, and 155-160°.

(c) In addition, polydopamine itself has excellent ultraviolet light absorption ability and photothermal conversion performance, and has a high degree of chemical and mechanical stability, which can further improve the weather resistance of the protective coating. The protective coating is tested through the actual artificial accelerated ultraviolet aging test The aging resistance can reach 7000h. At the same time, the protective coating has excellent wear resistance, corrosion resistance and anti-icing performance after film formation.

(d) The preparation process and process of the super-amphiphobic and super-weather-resistant silicone protective coating provided by the present invention are simple, the synthesis conditions are mild, and the requirements for equipment are relatively low, and more complicated etching methods, chemical vapor deposition methods, and electrospinning methods have obvious advantages compared to other.

Description of drawings

Fig. 1 is a schematic structural view of the super-amphiphobic super-weather-resistant organic silicon protective coating provided in Example 1 of the present invention;

Detailed ways

In order to make the technical solutions, advantages and achieved goals of the present invention clearer, the present invention will be described in detail below through specific examples. Non-essential equivalent changes or adjustments made in the content and spirit of the above invention all fall within the protection scope of the present invention.

One, synthesis embodiment:

Example 1

(1) Preparation of modified silicone resin:

Add hexyltriethoxysilane and 1H,1H-nonafluoro-1-pentanol into a three-necked flask at a ratio of 2:1 by mass and number at room temperature, stir and heat up to 60°C and react for 2 hours, then cool down and discharge , to obtain the modified silicone resin.

(2) Preparation of protective coating:

60 parts by mass of modified silicone resin, 20 parts by mass of polydopamine biomimetic modified palygorskite nanoparticles, 2.5 parts of cobalt naphthenate catalyst, 2 parts of silicone leveling agent, 1 part of dispersant, silicone defoamer 2 parts and 20 parts of butyl acetate solvent were respectively added into the paint mixing tank and stirred at a high speed under normal temperature to obtain a mixed paint. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Example 2

(1) Preparation of modified silicone resin:

Add octyltrimethoxysilane and 1H,1H-tridecafluoro-1-heptanol into a three-neck flask at a ratio of 1.5:1 in parts by mass at room temperature, stir to raise the temperature to 65°C and react for 2 hours, then cool down to release material to obtain the modified silicone resin.

(2) Preparation of protective coating:

76 parts by mass of modified silicone resin, 18 parts by mass of polydopamine biomimetic modified carbon nanotube nanoparticles, 0.2 parts of dibutyltin dilaurate catalyst, 1.5 parts of silicone leveling agent, 1.5 parts of dispersant, silicone defoaming agent Add 2.5 parts of solvent and 22 parts of cyclohexane solvent into the paint mixing tank respectively, and stir and mix at a high speed under normal temperature to obtain a mixed coating. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Example 3

(1) Preparation of modified silicone resin:

Add decyltriethoxysilane and 1H,1H-undecafluoro-1-hexanol into a three-necked flask at a ratio of 2:1 in parts by mass at room temperature, stir to raise the temperature to 70°C and react for 1.5h, then Cool down and discharge to obtain the modified silicone resin.

(2) Preparation of protective coating:

55 parts by mass of modified silicone resin, 24 parts by mass of polydopamine biomimetic modified titanium dioxide whisker nanoparticles, 2 parts of phthalate complex catalyst, 2.5 parts of silicone leveling agent, 2 parts of dispersant, silicone defoaming agent Add 2.5 parts of solvent and 24 parts of butyl acetate solvent into the paint mixing tank respectively, and stir and mix at a high speed at room temperature to obtain a mixed paint. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Example 4

(1) Preparation of modified silicone resin:

Add dodecyltrimethoxysilane and 1H,1H-pentadecafluoro-1-octanol into a three-neck flask at a ratio of 1.9:1 in parts by mass at room temperature, stir and raise the temperature to 70°C and react for 2 hours, then Cool down and discharge to obtain the modified silicone resin.

(2) Preparation of protective coating:

68 parts by mass of modified silicone resin, 25 parts by mass of polydopamine biomimetic modified carbon nanofiber nanoparticles, 0.5 part of stannous octoate, 2 parts of silicone leveling agent, 2 parts of dispersant, 2.5 parts of silicone defoamer and 28 parts of butanol solvent were respectively added into the paint mixing tank, and the mixed paint was obtained after stirring and mixing at a high speed under normal temperature conditions. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Example 5

(1) Preparation of modified silicone resin:

Add tetradecyltriethoxysilane and 1H,1H-nonadecafluoro-1-decanol into a three-necked flask at a ratio of 1.6:1 in parts by mass at room temperature, stir to raise the temperature to 75°C and react for 2 hours. Then the temperature is lowered and the material is discharged to obtain the modified silicone resin.

(2) Preparation of protective coating:

71 parts by mass of modified silicone resin, 20 parts by mass of polydopamine biomimetic modified carbon nanofiber nanoparticles, 1 part of tin naphthenate, 2 parts of silicone leveling agent, 1.5 parts of dispersant, 2.5 parts of silicone defoamer 25 parts and 25 parts of ethyl acetate solvent were respectively added into the paint mixing tank and stirred and mixed at a high speed under normal temperature to obtain a mixed paint. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Example 6

(1) Preparation of modified silicone resin:

Add hexadecyltrimethoxysilane and 1H,1H-heptadecafluoro-1-nonanol into a three-necked flask at a ratio of 2:1 in parts by mass at room temperature, stir to raise the temperature to 75°C and react for 2 hours, then Cool down and discharge to obtain the modified silicone resin.

(2) Preparation of protective coating:

89 parts by mass of modified silicone resin, 15 parts by mass of polydopamine biomimetic modified potassium titanate whisker nanoparticles, 2 parts of zinc naphthenate, 2 parts of silicone leveling agent, 1.5 parts of dispersant, silicone defoaming agent Add 2.5 parts of solvent and 15 parts of xylene solvent respectively into the paint mixing tank, and stir and mix at a high speed under normal temperature to obtain a mixed paint. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Example 7

(1) Preparation of modified silicone resin:

Add octadecyltriethoxysilane and 1H,1H-undecafluoro-1-hexanol into a three-necked flask at a ratio of 1.8:1 in parts by mass at room temperature, stir to raise the temperature to 80°C and react for 2 hours. Then the temperature is lowered and the material is discharged to obtain the modified silicone resin.

(2) Preparation of protective coating:

52 parts by mass of modified silicone resin, 25 parts by mass of polydopamine biomimetic modified carbon nanotube nanoparticles, 0.5 part of hexachlorocyclotriphosphazene, 2.5 parts of silicone leveling agent, 2 parts of dispersant, silicone defoaming agent Add 2.5 parts of solvent and 30 parts of butyl acetate solvent into the paint mixing tank respectively, and stir and mix at a high speed at room temperature to obtain a mixed paint. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Example 8

(1) Preparation of modified silicone resin:

Add pentadecyltrimethoxysilane and 1H,1H-pentadecafluoro-1-octanol into a three-necked flask at a ratio of 1.7:1 in parts by mass at room temperature, stir to raise the temperature to 65°C and react for 2 hours, then Cool down and discharge to obtain the modified silicone resin.

(2) Preparation of protective coating:

57 parts by mass of modified silicone resin, 16 parts by mass of polydopamine bionic modified palygorskite nanoparticles, 0.05 parts of lead naphthenate, 2.5 parts of silicone leveling agent, 2.5 parts of dispersant, 2.5 parts of silicone defoamer 18 parts and 18 parts of toluene solvent were respectively added into the paint mixing tank and mixed evenly at high speed under normal temperature conditions to obtain a mixed paint. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Comparative example 1

(1) Preparation of modified silicone resin:

Add hexyltriethoxysilane and 1H,1H-nonafluoro-1-pentanol into a three-necked flask at a ratio of 2:1 by mass and number at room temperature, stir and heat up to 60°C and react for 2 hours, then cool down and discharge , to obtain the modified silicone resin.

(2) Preparation of protective coating:

60 parts by mass of modified silicone resin, 20 parts by mass of palygorskite nanoparticles, 2.5 parts of cobalt naphthenate catalyst, 2 parts of silicone leveling agent, 1 part of dispersant, 2 parts of silicone defoamer and butyl acetate Add 20 parts of the ester solvent into the paint mixing tank respectively, stir and mix at a high speed at room temperature to obtain a mixed paint. Subsequently, the mixed paint is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature to prepare a corresponding organic silicon protective coating.

Comparative example 2

(1) Preparation of modified silicone resin:

At room temperature, add octyltrimethoxysilane and 1H,1H-tridecafluoro-1-heptanol into a three-necked flask at a ratio of 1.5:1 in parts by mass, stir to raise the temperature to 65°C and react for 2 hours, then cool down to release material to obtain the modified silicone resin.

(2) Preparation of protective coating:

76 parts by mass of modified silicone resin, 18 parts by mass of polydopamine formed by self-polymerization of pure dopamine hydrochloride, 0.2 parts of dibutyltin dilaurate catalyst, 1.5 parts of silicone leveling agent, 1.5 parts of dispersant, silicone defoamer 2.5 parts and 22 parts of cyclohexane solvent were respectively added into the paint mixing tank, stirred and mixed at a high speed under normal temperature conditions to obtain a mixed paint. Subsequently, the mixed paint is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature to prepare a corresponding organic silicon protective coating.

Comparative example 3

(1) Preparation of modified silicone resin:

Add decyltriethoxysilane and 1H,1H-undecafluoro-1-hexanol into the three-necked flask at a ratio of 3:1 by mass and number at room temperature, stir and raise the temperature to 70°C and react for 1.5h, then Cool down and discharge to obtain the modified silicone resin.

(2) Preparation of protective coating:

55 parts by mass of modified silicone resin, 24 parts by mass of polydopamine biomimetic modified titanium dioxide whisker nanoparticles, 2 parts of phthalate complex catalyst, 2.5 parts of silicone leveling agent, 2 parts of dispersant, silicone defoaming agent Add 2.5 parts of solvent and 24 parts of butyl acetate solvent into the paint mixing tank respectively, and stir and mix at a high speed at room temperature to obtain a mixed paint. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Comparative example 4

(1) Preparation of modified silicone resin:

Add decyltriethoxysilane and 1H,1H-undecafluoro-1-hexanol into the three-necked flask at a ratio of 1:1 by mass and number at room temperature, stir and heat up to 70°C and react for 1.5h, then Cool down and discharge to obtain the modified silicone resin.

(2) Preparation of protective coating:

55 parts by mass of modified silicone resin, 24 parts by mass of polydopamine biomimetic modified titanium dioxide whisker nanoparticles, 2 parts of phthalate complex catalyst, 2.5 parts of silicone leveling agent, 2 parts of dispersant, silicone defoaming agent Add 2.5 parts of solvent and 24 parts of butyl acetate solvent into the paint mixing tank respectively, and stir and mix at a high speed at room temperature to obtain a mixed paint. Subsequently, the mixed coating is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature, so as to obtain a silicone protective coating with super-amphiphobic and super-weather resistance properties.

Comparative example 5

At room temperature, 44.55 parts by mass of dodecyltrimethoxysilane, 23.45 parts by mass of 1H, 1H-pentadecafluoro-1-octanol (dodecyltrimethoxysilane and 1H, 1H-pentadecafluoro-1- Octanol is 1.9 according to the ratio of parts by mass: 1), 25 parts by mass of polydopamine biomimetic modified carbon nanofiber nanoparticles, 0.5 part of stannous octoate, 2 parts of silicone leveling agent, 2 parts of dispersant, silicone defoaming agent Add 2.5 parts of solvent and 28 parts of butanol solvent into the paint mixing tank respectively, and stir and mix at a high speed under normal temperature to obtain a mixed coating. Subsequently, the mixed paint is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature to prepare a corresponding organic silicon protective coating.

Comparative example 6

At room temperature, 71 parts by mass of tetradecyltriethoxysilane (removing 1H, 1H-nonadecafluoro-1-decanol), 20 parts by mass of polydopamine biomimetic modified carbon nanofiber nanoparticles, and 1 part by mass of tin naphthenate 2 parts of silicone leveling agent, 1.5 parts of dispersant, 2.5 parts of silicone defoamer and 25 parts of ethyl acetate solvent were added to the paint mixing tank and stirred at a high speed at room temperature to obtain a mixed coating. Subsequently, the mixed paint is sprayed on the surface of the steel plate and the concrete substrate after surface treatment, and dried and cured at room temperature to prepare a corresponding organic silicon protective coating.

2. Performance measurement of protective coating:

(1) Superhydrophobic and superoleophobic properties:

Drop a drop of deionized water, ethylene glycol, and hexadecane respectively on the protective coating surface prepared in the embodiment and the comparative example with a 20 μl syringe, and use a static hydrophobic angle measuring instrument to measure the effect of each protective coating on water, ethylene glycol and hexadecane respectively. Hexadecane contact angle.

(2) Resistance to artificial accelerated aging performance:

The protective coatings prepared in Examples and Comparative Examples were respectively placed in an accelerated aging tester (QUVTM), using a UV-A bulb (experimental conditions: 8 hours of radiation under the UV lamp, 4 hours of rain, and a temperature of 35-80 ° C. Inner circulation) after continuous 3000h, 5000h and 7000h tests respectively, the surface morphology of the coating was observed, and the contact angle of the protective coating to water, ethylene glycol and hexadecane after 7000h aging was tested at the same time.

(3) Wear resistance:

Adopt wear tester emery wheel surface to paste 800 mesh sandpapers to carry out wear resistance test respectively to the protective coating prepared by embodiment and comparative example, each rubber emery wheel load quality is 1kg, after the wear test of continuous 5000 revolutions under this condition, Observe the wear condition of the protective coating surface and test the contact angle of the worn protective coating to water, ethylene glycol and hexadecane.

(4) Adhesive properties:

The protective coatings prepared in the examples and comparative examples were sprayed on the surface treated ultra-high performance concrete test block and the surface of the steel plate, dried and cured for 7 days under standard conditions, and finally tested according to the GB/T 5210-2006 standard. The bond strength of the protective coating to the concrete base surface and the steel plate base surface is compared with the bond strength of protective coatings commonly used in the market such as acrylic, polyurethane, polyurea, alkyd resin, and silicone resin.

(5) Corrosion resistance:

The protective coatings prepared in the examples and comparative examples were respectively immersed in a sodium chloride solution with a mass fraction of 3.5% for immersion corrosion testing. The coatings were observed after continuous testing for 7 days, 14 days, 28 days and 56 days. The surface morphology of the protective coating was also tested for contact angles of water, ethylene glycol and hexadecane after immersion for 56 days.

The performance test results of the embodiments of the present invention and comparative examples are as follows:

The protective coating that embodiment 1-8 makes has excellent super-amphiphobic performance, anti-aging performance (after 7000h artificial accelerated aging test, phenomenons such as paint film do not take place pulverization, foaming, cracking, peeling off and coating still has Superhydrophobic and certain oleophobic properties), wear resistance (after a continuous 5000-rpm wear test, the surface of the protective coating is not obviously worn out and the coating still has superhydrophobic and certain oleophobic properties), high adhesion performance (the bonding strength of the metal base surface and the concrete base surface are greater than 10MPa and 4MPa respectively) and corrosion resistance (the coating has been tested for 7 days, 14 days, 28 days and 56 days respectively, and it is found that there is no obvious corrosion on the surface of the coating. bulging, pulverization, cracking and other phenomena, the coating still has super-amphiphobic properties after 56 days of testing). In Comparative Example 1, due to the unmodified nanoparticles, the bonding strength between the coating and the surface of the substrate and the degree of crosslinking of the coating itself are significantly reduced, which makes the wear resistance, bonding strength and corrosion resistance of the coating better than those of the examples. Compared with 1, there is an obvious downward trend; in the comparative example 2, there is no fibrous or filamentous nano-particles, only the polydopamine formed by the self-polymerization of pure dopamine hydrochloride, and the prepared coating does not have the function of super amphiphobic; In comparative examples 3 and 4, the ratio of mass and number of silicone resin to fluorocarbon alcohol exceeds the specified range, and there is a certain degree of gap in the performance of the coating compared with the examples; in comparative example 5, the fluorocarbon alcohol After direct blending, the film-forming property of the coating is poor, and it does not have super-oleophobic function, and its durability and bonding performance are poor; after the fluorocarbon alcohol is removed in Comparative Example 6, the coating does not have super-oleophobic function , the aging resistance performance is significantly reduced.

Claims (8)

1. A super-amphiphobic super-weather-resistant silicone protective coating, characterized in that its raw material components and parts by weight of each component include as follows: 30-60 parts of silicone resin, Fluorocarbon alcohol 20-30 parts, 15-25 parts of polydopamine biomimetic modified nanoparticles; The silicone resin is trimethoxyl or triethoxysilane containing long-chain alkyl groups, wherein the number of carbon atoms in the long-chain alkyl groups is 6-18; The fluorocarbon alcohol is a straight-chain fluorocarbon alcohol with 5-10 carbon atoms and no fluorine group on the carbon atom directly connected to the hydroxyl group; The nanoparticles in the polydopamine biomimetic modified nanoparticles are fibrous rod-like or filamentary structures, selected from one or more of carbon nanotubes, carbon nanofibers, palygorskite, titanium dioxide whiskers, and potassium titanate whiskers. kind of mix; The mass ratio of the silicone resin to the fluorocarbon alcohol is (1.5-2):1. 2. according to the described super-amphiphobic super-weather-resistant organic silicon protective coating of claim 1, it is characterized in that, its raw material component and each component parts by weight also include as follows: Catalyst 0.01-2.5 parts, Silicone leveling agent 1-3 parts, Dispersant 0.5-2 parts, Silicone defoamer 0.5-3 parts, 15-30 parts of organic solvent; The catalyst is any one of naphthenates or carboxylates of Pb, Fe, Zn, Sn, Co, etc., phosphazene chloride and phthalate complexes. 3. according to claim 1 and 2 described super-amphiphobic super-weather-resistant organosilicon protective coating, it is characterized in that, the quality of described organosilicon resin, fluorocarbon alcohol and polydopamine biomimetic modified nanoparticles three and account for the total mass 65%-85%. 4. according to the described super-amphiphobic super-weather-resistant organic silicon protective coating of claim 1, it is characterized in that, described fluorocarbon alcohol is selected from 1H, 1H-nonafluoro-1-pentanol, 1H, 1H-undecafluoro- 1-Hexanol, 1H, 1H-Tridecafluoro-1-heptanol, 1H, 1H-Pentadecafluoro-1-octanol, 1H, 1H-Heptadecafluoro-1-nonanol, 1H, 1H-Nadecafluoro-1-octanol Any one of fluoro-1-decanol. 5. The super-amphiphobic and super-weather-resistant silicone protective coating according to claim 1, characterized in that, the particle diameter of the nanoparticles is 25-100nm. 6. according to the described super-amphiphobic super-weather-resistant organosilicon protective coating of claim 2, it is characterized in that, described catalyst is selected from lead naphthenate, iron naphthenate, zinc naphthenate, tin naphthenate, naphthenate Any one of cobaltate, dibutyltin dilaurate, stannous octoate, hexachlorocyclotriphosphazene, and titanate complexes. 7. according to the described super-amphiphobic super-weather-resistant organic silicon protective coating of claim 2, it is characterized in that, described organic solvent is one in toluene, xylene, cyclohexane, ethyl acetate, butyl acetate, butanol a mixture of one or more. 8. The preparation method of the super-amphiphobic super-weather-resistant organic silicon protective coating described in any one of claims 1-7, is characterized in that, concrete steps are as follows: (1) Preparation of modified silicone resin: Add silicone resin and fluorocarbon alcohol into the reaction vessel, stir and heat up to 60-80°C, and continue to react at this temperature for 1-2 h to obtain modified silicone resin ; (2) Add the modified silicone resin, polydopamine biomimetic modified nanoparticles, catalyst, silicone leveling agent, dispersant, silicone defoamer and solvent into the paint mixing tank and stir at a high speed at room temperature Obtain a kind of super-amphiphobic super-weather-resistant organosilicon protective coating after mixing evenly; (3) Spray the protective coating obtained in step (2) on the surface of the substrate after surface treatment, and cure and dry under normal temperature conditions to obtain a silicone protective coating with super amphiphobic and super weather resistance properties.