Preparation method and application of super-hydrophobic, transparent and durable coating
Technical Field
The invention belongs to the technical field of composite hydrophobic materials, and particularly relates to a preparation method and application of a super-hydrophobic, transparent and durable coating.
Background
The super-hydrophobic surface is a novel special surface with a static contact angle larger than 150 degrees and a rolling angle smaller than 10 degrees, is closely related to human life, has wide application value, has the characteristics of self-cleaning, antifogging, waterproofing, anti-icing, drag reduction, corrosion resistance, oil-water separation and the like, has very wide application prospect in the fields of buildings, electronics, energy, aviation and textiles, and can be used for carrying out targeted research and development on the super-hydrophobic coating according to the characteristics and requirements of different fields. After the principle of lotus leaf effect is disclosed since the teaching of Barthlott in 1997, researchers have more profound understanding on the wetting behavior of the material surface, and also further research on the construction mechanism of super-hydrophobicity and reach the consensus: firstly, the surface is constructed with certain roughness, and secondly, the surface is modified by chemical substances with low surface energy.
CN111154396A discloses a nano-silica modified silicon resin super-hydrophobic coating, a preparation method and an application thereof, wherein the nano-silica modified silicon resin super-hydrophobic coating is formed by grafting hydrophobic functional group molecules with low surface energy and high stability on the surface of nano-silica particles and then crosslinking the molecules with silicon resin, the formed nano-silica modified silicon resin super-hydrophobic coating has a super-hydrophobic surface with low surface energy and a micro-nano binary coarse structure, and the static contact angle of the super-hydrophobic coating is 159.6-161.8 degrees.
CN107868533B discloses a super-hydrophobic coating and a method for preparing a durable super-hydrophobic coating thereof, comprising: (1) primer coating: consists of 40 to 70 percent of fluororesin, 5 to 20 percent of curing agent, 0 to 10 percent of nano particles and 15 to 45 percent of solvent; (2) finishing paint: consists of fluororesin 4-30 wt%, curing agent 1-10 wt%, nanometer particle 2-10 wt% and solvent 75-85 wt%. And spraying the primer to the surfaces of different base materials, curing for a certain time at room temperature, then spraying the finish, and curing for 2-7 days at room temperature to obtain the super-hydrophobic coating film with good hardness, adhesion, flexibility, impact resistance, wear resistance, acid and alkali resistance and salt resistance. The super-hydrophobic coating material obtained by the super-hydrophobic coating has high durability and substrate universality, is suitable for large-area construction, and enables the surfaces of metal, glass, stone, wood, fabric and the like to have excellent self-cleaning, waterproof, acid and alkali resistance and corrosion resistance.
However, in the prior art, a super-hydrophobic coating with high transparency, good adhesive force, wear resistance, acid resistance, heat resistance and water resistance is not prepared efficiently and massively under the condition of low energy consumption by a simple process. The normal-temperature cured super-hydrophobic coating prepared based on the sol-gel method and the spin coating technology has more excellent mechanical stability, durability, hydrophobicity, transparency and other properties.
Disclosure of Invention
To solve some problems of the prior art, the present invention aims to provide a preparation method of a super-hydrophobic, transparent and durable coating and potential application thereof. The coating has high transparency, mechanical stability, durability and substrate universality, can be applied to the surfaces of glass, ceramics, conductive glass, aluminum, fabrics, ABS plastics and the like in a large area, and greatly improves the hydrophobicity.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a transparent super-hydrophobic coating, which comprises room temperature curing resin, a solvent and modified nanoparticles. The room temperature cured resin provides mechanical properties and partial special properties of the coating, so that the coating has certain mechanical strength, substrate bonding force, good transparency and good hydrophobicity (107 degrees). The modified nanoparticles have low surface energy grafts and high surface roughness. And combining the two to obtain uniform nano particle/resin composite super-hydrophobic coating dispersion liquid, coating the dispersion liquid on the surface of a machine body in a spin coating or spraying mode, and curing at room temperature for 24 hours to obtain the super-hydrophobic coating with excellent performance.
The super-hydrophobic, transparent and durable coating comprises room temperature curing resin, solvent and modified nano particles in the following mass ratio:
the coating comprises 14% -50% of room temperature curing resin, 50% -85% of solvent and 0.25% -3% of modified nanoparticles.
The 14-50% of room temperature curing resin comprises 0-75% of optional silane and 25-100% of essential silane;
further, 0-75% of the optional silane in the 14-50% room temperature curing resin comprises one or more of phenyl silane, isobutyl silane, propyl silane, 3- (methacryloyloxy) propyl silane, mercapto silane, octadecyl silane, hexadecyl silane, methyl silane, chloropropyl silane, tetramethoxy silane, and polydimethylsiloxane (hydroxyl terminated). 25% to 100% of essential silanes including 50% to 75% of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 25% to 38% of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3% to 25% of perfluorodecyltrimethoxysilane;
further, the catalyst of the 14-50% room temperature curing resin is dibutyl tin dilaurate, and the resin is a net structure with long fluorine-based chains, epoxy groups and silicon-oxygen chains. The long fluorine-based chain can reduce the surface energy of the resin, the epoxy group and the silicon-oxygen chain can interact with the silicon-oxygen bond of the substrate, so that the bonding force between the resin and the substrate is enhanced, and meanwhile, the epoxy group can chemically react with the amino group, so that the mechanical property of the resin is improved.
The 50-85% solvent includes but is not limited to methanol, ethanol, tetrahydrofuran, toluene, ethyl acetate, chloroform.
The 0.25-3% modified nano particles comprise 80-98% nano particles and 2-20% surface modifier;
further, 80% -98% of the 0.25% -3% modified nanoparticles include, but are not limited to, micro/nano-sized silicon dioxide, titanium dioxide, zirconium dioxide, polymer nanoparticles, and the like. 2% -20% of surface modifying agents include but are not limited to heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltriethoxysilane, octadecyltrimethoxysilane, hexadecyltrimethoxysilane.
The invention provides a preparation method of a transparent super-hydrophobic coating, which comprises the following steps:
step (1): an amount of optional silane, 3- (2, 3-glycidoxy) propyltrimethoxysilane and dibutyl tin dilaurate were mixed in a glass flask and stirred for 30min, and then the mixed solution was aged at room temperature for a certain period of time. Then adding a certain amount of perfluorodecyl trimethoxy silane into the solution and stirring for 30min to form chain siloxane. Finally, adding a certain amount of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane into the mixed solution, stirring for ten minutes, and standing to obtain the room-temperature curing resin.
Preferably, the mass ratio of the optional silane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, dibutyl tin dilaurate, perfluorodecyl trimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane in the step (1) is (50-80): (12-20): (0.2-0.5): (0.1-0.2): (6-10). A further preferred mass ratio is 75: 16: 0.35: 0.15: 8.5.
Step (2): dispersing nano and surface modifier in certain amount of solvent. Stirring for a period of time at room temperature at a certain rotating speed, and carrying out ultrasonic treatment for a certain period of time to obtain a uniformly dispersed nano particle suspension.
Preferably, the mass ratio of the nano particles to the surface modification in the step (2) is 12:1, the stirring time is 1-3h, and the ultrasonic time is 1-2 h.
And (3): and (3) mixing the resin prepared in the step (1) and the nano particle suspension prepared in the step (2) according to a certain mass ratio, and performing ultrasonic treatment for a certain time to obtain a uniform mixed solution.
Preferably, the mass ratio of the resin to the nanoparticle suspension is 1: (1-6) the ultrasonic treatment time is 5-15 min.
And (4): and (4) coating the uniform mixed solution prepared in the step (3) on a substrate by using a spin coating or spray coating method, and standing at room temperature for 24 hours to obtain the super-hydrophobic, transparent and durable coating.
Preferably, the spin coating method: the substrate was placed on a spin coater, spin coater parameters were set at 500rmp,10s and 1000rmp,10s, and the mixed liquid was dropped onto the substrate for spin coating. The spraying method comprises the following steps: placing the prepared mixed solution in a spray gun, keeping the distance between the spray nozzle and the surface of the base material at 20-30cm, the diameter of the spray nozzle at 0.5mm, and the pressure of the spray gun at 0.15MPa, and spraying the mixed solution on the surface of the matrix.
The low surface energy modification of the nanoparticles is realized by grafting and modifying low surface energy molecules on the surfaces of the nanoparticles, and the modified nanoparticles are mixed with the resin with excellent mechanical property solidified at room temperature to obtain uniform dispersion liquid. The dispersion is deposited on the surface of a matrix in a spin coating or spray coating mode, and the super-hydrophobic, transparent and durable coating is prepared. The prepared super-hydrophobic coating has the characteristics of simple method operation, low energy consumption, high efficiency and the like, and has excellent properties of transparency, super-hydrophobicity, good adhesive force, durability, self-cleaning and the like, so that the coating has wide market application prospect.
Drawings
FIG. 1 shows the surface water drop morphology of the superhydrophobic coating of example 8.
FIG. 2 is an SEM image of the surface of the superhydrophobic coating of example 8.
Fig. 3 is a schematic diagram of self-cleaning in example 8.
The specific implementation mode is as follows:
example 1:
step (a): 4.277g of optional silane, 0.945g of 3- (2, 3-glycidoxy) propyltrimethoxysilane, and 0.06g of dibutyltin dilaurate were added in this order to a 25mL beaker and stirred for 30min, and the solution was aged at room temperature for 24 h. Then 0.0034g of perfluorodecyltrimethoxysilane was added to the solution and stirred for 30 min. Subsequently, 0.445g of curing agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added and stirred for 10min to form a stable mixture.
Step (b): in a 50ml flask, 0.9g of SiO2Nanoparticles and 0.072g perfluorodecyltrimethoxysilane were dispersed in 30g ethanol, and the mixture was stirred for 1.5h and sonicated for 1h to give a stable suspension.
Step (c): mixing the mixed liquid prepared in the step (a) and the suspension prepared in the step (b) according to the mass ratio of 1: 1, and carrying out ultrasonic treatment for 5min to form a uniform mixture.
Step (d): and (c) coating the mixture prepared in the step (c) on a substrate in a spin coating or spray coating mode to prepare the super-hydrophobic, transparent and durable coating.
Example 2:
step (a): 4.277g of optional silane, 0.945g of 3- (2, 3-glycidoxy) propyltrimethoxysilane, and 0.06g of dibutyltin dilaurate were added in this order to a 25mL beaker and stirred for 30min, and the solution was aged at room temperature for 24 h. Then 0.0034g of perfluorodecyltrimethoxysilane was added to the solution and stirred for 30 min. Subsequently, 0.445g of curing agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added and stirred for 10min to form a stable mixture.
Step (b): in a 50mL flask, 0.9g of SiO2Nanoparticles and 0.072g perfluorodecyltrimethoxysilane were dispersed in 30g ethanol, and the mixture was stirred for 1.5h and sonicated for 1h to give a stable suspension.
Step (c): mixing the mixed liquid prepared in the step (a) and the suspension prepared in the step (b) according to the mass ratio of 1: 2, and carrying out ultrasonic treatment for 5min to form a uniform mixture.
Step (d): and (c) coating the mixture prepared in the step (c) on a substrate in a spin coating or spray coating mode to prepare the super-hydrophobic, transparent and durable coating.
Example 3:
step (a): 4.277g of optional silane, 0.945g of 3- (2, 3-glycidoxy) propyltrimethoxysilane, and 0.06g of dibutyltin dilaurate were added in this order to a 25mL beaker and stirred for 30min, and the solution was aged at room temperature for 24 h. Then 0.0034g of perfluorodecyltrimethoxysilane was added to the solution and stirred for 30 min. Subsequently, 0.445g of curing agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added and stirred for 10min to form a stable mixture.
Step (b): in a 50mL flask, 0.9g of SiO2Nanoparticles and 0.072g perfluorodecyltrimethoxysilane were dispersed in 30g ethanol, and the mixture was stirred for 1.5h and sonicated for 1h to give a stable suspension.
Step (c): mixing the mixed liquid prepared in the step (a) and the suspension prepared in the step (b) according to the mass ratio of 1: 3, and carrying out ultrasonic treatment for 5min to form a uniform mixture.
Step (d): and (c) coating the mixture prepared in the step (c) on a substrate in a spin coating or spray coating mode to prepare the super-hydrophobic, transparent and durable coating.
Example 4:
step (a): 4.277g of optional silane, 0.945g of 3- (2, 3-glycidoxy) propyltrimethoxysilane, and 0.06g of dibutyltin dilaurate were added in this order to a 25mL beaker and stirred for 30min, and the solution was aged at room temperature for 24 h. Then 0.0034g of perfluorodecyltrimethoxysilane was added to the solution and stirred for 30 min. Subsequently, 0.445g of curing agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added and stirred for 10min to form a stable mixture.
Step (b): in a 50mL flask, 0.9g of SiO2Nanoparticles and 0.072g perfluorodecyltrimethoxysilane were dispersed in 30g ethanol, and the mixture was stirred for 1.5h and sonicated for 1h to give a stable suspension.
Step (c): mixing the mixed liquid prepared in the step (a) and the suspension prepared in the step (b) according to the mass ratio of 1: 4, and carrying out ultrasonic treatment for 5min to form a uniform mixture.
Step (d): and (c) coating the mixture prepared in the step (c) on a substrate in a spin coating or spray coating mode to prepare the super-hydrophobic, transparent and durable coating.
Example 5:
step (a): 4.277g of optional silane, 0.945g of 3- (2, 3-glycidoxy) propyltrimethoxysilane, and 0.06g of dibutyltin dilaurate were added in this order to a 25mL beaker and stirred for 30min, and the solution was aged at room temperature for 24 h. Then 0.0034g of perfluorodecyltrimethoxysilane was added to the solution and stirred for 30 min. Subsequently, 0.445g of curing agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added and stirred for 10min to form a stable mixture.
Step (b): in a 50mL flask, 1.5g of SiO2Dispersing the nano particles and 0.12g of perfluorodecyl trimethoxy silane into 30g of ethanol, stirring the mixture for 1.5h, and carrying out ultrasonic treatment for 1h to obtain the nano-particleTo a stable suspension.
Step (c): mixing the mixed liquid prepared in the step (a) and the suspension prepared in the step (b) according to the mass ratio of 1: 1, and carrying out ultrasonic treatment for 5min to form a uniform mixture.
Step (d): and (c) coating the mixture prepared in the step (c) on a substrate in a spin coating or spray coating mode to prepare the super-hydrophobic, transparent and durable coating.
Example 6:
step (a): 4.277g of optional silane, 0.945g of 3- (2, 3-glycidoxy) propyltrimethoxysilane, and 0.06g of dibutyltin dilaurate were added in this order to a 25mL beaker and stirred for 30min, and the solution was aged at room temperature for 24 h. Then 0.0034g of perfluorodecyltrimethoxysilane was added to the solution and stirred for 30 min. Subsequently, 0.445g of curing agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added and stirred for 10min to form a stable mixture.
Step (b): in a 50mL flask, 0.9g of SiO2Nanoparticles and 0.072g perfluorodecyltrimethoxysilane were dispersed in 30g ethanol, and the mixture was stirred for 1.5h and sonicated for 1h to give a stable suspension.
Step (c): mixing the mixed liquid prepared in the step (a) and the suspension prepared in the step (b) according to the mass ratio of 1: 2, and carrying out ultrasonic treatment for 5min to form a uniform mixture.
Step (d): and (c) coating the mixture prepared in the step (c) on a substrate in a spin coating or spray coating mode to prepare the super-hydrophobic, transparent and durable coating.
Example 7:
step (a): 4.277g of optional silane, 0.945g of 3- (2, 3-glycidoxy) propyltrimethoxysilane, and 0.06g of dibutyltin dilaurate were added in this order to a 25mL beaker and stirred for 30min, and the solution was aged at room temperature for 24 h. Then 0.0034g of perfluorodecyltrimethoxysilane was added to the solution and stirred for 30 min. Subsequently, 0.445g of curing agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added and stirred for 10min to form a stable mixture.
Step (b): at 5In a 0mL flask, 0.9g of SiO2Nanoparticles and 0.072g perfluorodecyltrimethoxysilane were dispersed in 30g ethanol, and the mixture was stirred for 1.5h and sonicated for 1h to give a stable suspension.
Step (c): mixing the mixed liquid prepared in the step (a) and the suspension prepared in the step (b) according to the mass ratio of 1: 3, and carrying out ultrasonic treatment for 5min to form a uniform mixture.
Step (d): and (c) coating the mixture prepared in the step (c) on a substrate in a spin coating or spray coating mode to prepare the super-hydrophobic, transparent and durable coating.
Example 8:
step (a): 4.277g of optional silane, 0.945g of 3- (2, 3-glycidoxy) propyltrimethoxysilane, and 0.06g of dibutyltin dilaurate were added in this order to a 25mL beaker and stirred for 30min, and the solution was aged at room temperature for 24 h. Then 0.0034g of perfluorodecyltrimethoxysilane was added to the solution and stirred for 30 min. Subsequently, 0.445g of curing agent N- (2-aminoethyl) -3-aminopropyltrimethoxysilane was added and stirred for 10min to form a stable mixture.
Step (b): in a 50mL flask, 0.9g of SiO2Nanoparticles and 0.072g perfluorodecyltrimethoxysilane were dispersed in 30g ethanol, and the mixture was stirred for 1.5h and sonicated for 1h to give a stable suspension.
Step (c): mixing the mixed liquid prepared in the step (a) and the suspension prepared in the step (b) according to the mass ratio of 1: 4, and carrying out ultrasonic treatment for 5min to form a uniform mixture.
Step (d): and (c) coating the mixture prepared in the step (c) on a substrate in a spin coating or spray coating mode to prepare the super-hydrophobic, transparent and durable coating.
Example 8 test data
Serial number
|
Inspection item
|
Technical index
|
1
|
Appearance of the product
|
Even and white
|
2
|
Contact angle
|
160.1°
|
3
|
Transmittance (200 ion 800nm)
|
93.6%
|
4
|
Adhesion force
|
The contact angle was maintained at 140 ° after 200 cycles of the tape application test
|
5
|
Chemical resistance (PH 1,7,14)
|
After dipping for 40min, the hydrophobic angle of the coating soaked by only the alkaline solution is obviously reduced
|
6
|
Heat resistance
|
After the heat preservation at 200 ℃ for 4 hours, the hydrophobic angle has no obvious change, and the film turns slightly yellow
|
7
|
Resistance to ultraviolet aging
|
No significant change in the hydrophobic angle after 7 days of testing according to ASTM D4587
|
8
|
Impact resistance
|
The contact angle is kept at 135 DEG after 6000 water drop impact test
|
9
|
Applications of
|
Can be applied to self-cleaning and oil-water separation |
From the above examples, it can be seen that the super-hydrophobic coating with high durability prepared by the super-hydrophobic coating of the present invention has a coating contact angle of 160.1 °, a high transmittance (93.6), good adhesion, durability to acid, ultraviolet, impact and high temperature, and potential application value. In conclusion, the super-hydrophobic, transparent and durable coating is prepared by a simple process method.