CN109943213B - Preparation method of environment-friendly super-hydrophobic coating with high mechanical durability - Google Patents
Preparation method of environment-friendly super-hydrophobic coating with high mechanical durability Download PDFInfo
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Abstract
The invention discloses a preparation method of an environment-friendly super-hydrophobic coating with high mechanical durability, and belongs to the technical field of preparation of coatings. The preparation method comprises the following steps: firstly, waste edible oil after filtration and purification is taken as a raw material, waste edible oil fatty amide is synthesized through an amino decomposition reaction, then waste edible oil fatty amide and toluene diisocyanate are taken as raw materials, a polyurethane prepolymer is prepared by adopting a one-step method, then the polyurethane prepolymer is blocked by double-end type amino-hydrocarbon-based silicone oil to obtain modified polyurethane, finally, the organic silicon modified polyurethane and hydrophobic treated silicon carbide particles are mixed, sprayed on a substrate after magnetic stirring, dried and cured to obtain the organic silicon modified polyurethane. The coating prepared by the method is low in cost and environment-friendly, has good heat conduction, wear resistance and self-cleaning performance, can solve the problem of dust pollution related to the fins of the mining air cooler, and ensures the heat exchange efficiency of the air cooler in the using process.
Description
Technical Field
The invention relates to the technical field of preparation of coatings, in particular to a preparation method of an environment-friendly super-hydrophobic coating.
Background
Because of the long term mining, shallow coal seams have been depleted and most coal mines have to mine deep coal seams. As the mining depth increases, the surrounding rock temperature also rises, resulting in an increasing risk of thermal damage in mining operations. For high-temperature mines, the problem of high-temperature heat damage cannot be solved only by mine ventilation under the general condition. In order to ensure the proper working of the staff, corresponding cooling systems must be built in most cases. Along with the innovation of the technology, the air cooler cooling technology is widely applied to the coal mining industry and becomes one of the main means for reducing the high temperature of the mine. The mining air cooler is generally arranged on an underground mining working surface or an air inlet roadway of the working surface, and underground air is seriously polluted, has more coal dust, high temperature and high humidity and is narrow in space. The severe working environment of the mine makes the surfaces of the fins easy to accumulate dust, and the heat exchange effect of the air cooler is seriously influenced.
Superhydrophobic surfaces have attracted great interest in academia and industry due to their potential applications in the fields of self-cleaning, anti-icing and anti-corrosion. Most modern coatings are synthesized to provide a hydrophobic/superhydrophobic surface. There are two essential requirements for the manufacture of hydrophobic coatings: one is a low surface energy material, and the other is a micro-nano layered structure. The super-hydrophobic coating has poor adhesion force between the low surface energy component and the base material, the micro-nano structure is very fragile, when the surface is impacted, mechanical actions such as friction and the like are easily damaged, the super-hydrophobic performance is lost, and the super-hydrophobic coating without high mechanical performance is difficult to play a role in practical application.
At present, the preparation of the super-hydrophobic coating/layer related to the prior art mainly comprises the following steps:
CN108505319A discloses an environment-friendly super-hydrophobic material, a preparation method and an application thereof, wherein a nano material is mainly used for modifying the integral three-dimensional structure of a substrate material, so that the roughness of the integral three-dimensional structure of the substrate material is improved, and the super-hydrophobic material with excellent hydrophobic property is prepared, and the main research method is as follows: dissolving ferric trichloride, urea and sodium dodecyl sulfate in deionized water to obtain a mixed solution, then adding the mixed solution and a substrate material into a Teflon-lined high-pressure kettle for hydrothermal reaction, naturally cooling to room temperature, washing with the deionized water, and drying to obtain an environment-friendly super-hydrophobic material;
CN109207023A discloses a controllable preparation method of an environment-friendly hydrophobic coating on the surface of an aviation material, which comprises the following steps: dissolving epoxy resin with acetone, spraying the dissolved epoxy resin on a treated aviation material substrate to obtain an adhesive layer, mechanically stirring and uniformly mixing zinc stearate powder and epoxy resin, adding a curing agent, adding a proper amount of acetone, uniformly mixing, spraying the mixture on the adhesive layer, drying an obtained coating sample at room temperature, etching the coating sample in an acetic acid solution, cleaning and drying, modifying the coating sample in an absolute ethyl alcohol solution of stearic acid, and drying to obtain a hydrophobic coating;
CN107880770A discloses a preparation method of an environment-friendly multifunctional super-hydrophobic coating, which mainly comprises the steps of preparing nano titanium dioxide powder, preparing octadecyl isocyanate modified nano titanium dioxide powder, preparing a mixed coating of silicone resin and modified nano titanium dioxide powder, and coating the obtained hydrophobic coating on a substrate to obtain the super-hydrophobic coating.
The super-hydrophobic coatings in the prior art all have super-hydrophobicity, however, the mechanical durability of the coatings cannot meet the requirements, and as fossil resources are exhausted and environmental awareness of people is improved, more and more attention is paid to manufacturing bio-based polymers by using more sustainable and environmentally-friendly raw materials. In view of the above, there is a need to develop an environmentally friendly superhydrophobic coating having high mechanical durability.
Disclosure of Invention
In order to solve the main technical problem of poor mechanical property of the super-hydrophobic coating in the prior art, the invention provides a preparation method of an environment-friendly super-hydrophobic coating with high mechanical durability, and the coating prepared by the method has excellent mechanical durability.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of an environment-friendly super-hydrophobic coating sequentially comprises the following steps:
a, preparing the waste edible oil fatty amide,
taking filtered and purified waste edible oil as a raw material, and synthesizing waste edible oil fatty amide through an amino decomposition reaction;
b, preparing a polyurethane prepolymer,
dissolving waste edible oil fatty amide in acetone at room temperature to obtain a 50 wt% waste edible oil fatty amide solution, adding the waste edible oil fatty amide solution into toluene diisocyanate, and stirring at a certain temperature by using dibutyltin dilaurate as a catalyst to obtain a polyurethane prepolymer, wherein the pourable viscosity is reached;
c, preparing the modified polyurethane by the method,
carrying out end capping on the polyurethane prepolymer by using double-end type amino-hydrocarbon silicone oil to prepare modified polyurethane;
d, preparing the environment-friendly super-hydrophobic coating,
hydrophobic silicon carbide powder is obtained by carrying out hydrophobic treatment on silicon carbide particles, then the modified polyurethane is mixed with the hydrophobic silicon carbide powder, is sprayed on a substrate after being magnetically stirred, and is dried and cured to obtain the modified polyurethane;
in the step d, the hydrophobic treatment step is as follows: dispersing silicon carbide particles in an ethanol solution through ultrasonic treatment, then adding double-end type amino-hydrocarbon silicone oil, magnetically stirring at a certain temperature to obtain a modified nano silicon carbide solution, and centrifugally washing and drying to obtain hydrophobic silicon carbide powder;
the mass ratio of the hydrophobic silicon carbide powder to the modified polyurethane is 2-10: 1.
In a preferred embodiment of the present invention, in step a, the preparation of the waste edible oil fatty amide comprises the following steps: firstly, putting sodium methoxide and diethanolamine into a reaction bottle, turning on a heating switch and a magnetic stirring device, heating and stirring for 20 minutes at 80 ℃, then dropwise adding purified waste edible oil within 60 minutes, completely adding the purified waste edible oil, raising the reaction temperature to 120 ℃, and continuously stirring and reacting for 3 hours at the temperature to obtain the sodium methoxide, diethanolamine and waste edible oil, wherein the molar ratio of the sodium methoxide to the waste edible oil to the diethanolamine is 1:45: 15.
As another preferable scheme of the invention, in the step b, the waste edible oil fatty amide and the toluene diisocyanate are stirred for 2 hours at 70 ℃ at a molar ratio of 1:1.2 to reach a pourable viscosity.
Further, in the step c, dropwise adding the double-end amino alkyl silicone oil into the polyurethane prepolymer, adjusting the viscosity of the system by using acetone, and continuously stirring and reacting for 3 hours at 55 ℃ to obtain the modified polyurethane; the molar ratio of the polyurethane prepolymer to the double-end amino-hydrocarbon silicone oil is 1: 2.
Further, in the hydrophobic treatment step, silicon carbide particles are dispersed in an ethanol solution through ultrasonic treatment for 30min, then the double-end type amino hydrocarbon-based silicone oil is added, and magnetic stirring is carried out for 4h at 70 ℃.
Furthermore, the double-end type amino hydrocarbon silicone oil is synthesized by hydroxyl polydimethylsiloxane and 3-aminopropyl triethoxysilane.
Furthermore, in the step d, the particle size of the silicon carbide particles is 30-100 nm, and the particle shape is spherical.
Further, the mass ratio of the silicon carbide particles to the ethanol solution to the double-end amino-hydrocarbon-based silicone oil is 2:3:10 in sequence, and the drying temperature is 130 ℃.
Further, the substrate is glass, copper, aluminum or iron.
The reaction mechanism of the present invention is briefly described below, and the reaction equation of the modified polyurethane is as follows:
compared with the prior art, the invention has the following beneficial technical effects:
in the aspect of raw material selection, the waste edible oil is used as a raw material, so that the waste is treated, the pollution to the environment is reduced, and the method is low in price and environment-friendly;
in the aspect of the preparation method, the polyurethane prepolymer is terminated by adopting the double-end amino-hydrocarbon silicone oil, so that the crosslinking capability of polyurethane is improved, and the bonding capability of the coating and the substrate is further enhanced; the silicon carbide particles with excellent physical properties are used as fillers to improve the mechanical durability of the coating, in order to avoid agglomeration, the silicon carbide particles are subjected to hydrophobic treatment, the nano silicon carbide subjected to hydrophobic treatment has good dispersibility and can be uniformly distributed in modified polyurethane, a rough micro-nano surface is created, the hydrophobic property of the coating is further improved, volatile acetone is used as a solvent, and the coating is basically free of residues after being formed; the environment-friendly super-hydrophobic coating prepared by the invention has good mechanical properties, and contact angles of the coating to water drops are measured to be more than 150 degrees by carrying out contact angle test through a DSA100 contact angle analyzer after a sand paper abrasion test.
It should be specifically noted that the application significantly improves the hydrophobic property of the coating by subjecting the silicon carbide particles to hydrophobic treatment, and the specific results are shown in comparative example 1.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a flow chart of a process for preparing an environmentally friendly superhydrophobic coating according to the present invention;
FIG. 2 is an infrared spectrum of waste edible oil fatty acid amide;
FIG. 3 is an infrared spectrum of a polyurethane prepolymer;
FIG. 4 is an infrared spectrum of the modified polyurethane;
FIG. 5 is a scanning electron micrograph of a superhydrophobic coating prepared in example 1;
FIG. 6 is a graph showing the relationship between the contact angle and the number of wear times according to the embodiment of the present invention.
Detailed Description
The invention provides a preparation method of an environment-friendly super-hydrophobic coating with high mechanical durability, and in order to make the advantages and technical scheme of the invention clearer and clearer, the invention is described in detail with reference to specific embodiments.
The raw materials selected by the invention can be purchased and obtained through commercial channels.
The preparation method of the environment-friendly super-hydrophobic coating with high mechanical durability comprises the steps of firstly preparing polyurethane prepolymer by using purified waste edible oil, then carrying out end capping on the polyurethane prepolymer by using double-end type amino-hydrocarbon-based silicone oil to obtain modified polyurethane, finally mixing the modified polyurethane with hydrophobic treated silicon carbide particles, and spraying to obtain the environment-friendly super-hydrophobic coating with high mechanical durability, as shown in figure 1.
Example 1:
firstly, putting sodium methoxide (0.007mol) and diethanolamine (0.32mol) into a three-neck round-bottom flask, turning on a heating switch and a magnetic stirring device, heating and stirring at 80 ℃ for 20 minutes, and then dropwise adding purified waste edible oil (0.1mol) within 60 minutes. After the purified waste edible oil is completely added, raising the reaction temperature to 120 ℃, and continuously stirring and reacting for 3 hours at the temperature to obtain waste edible oil fatty amide;
step two, preparing a polyurethane prepolymer, namely preparing the polyurethane prepolymer by using waste edible oil fatty amide and toluene diisocyanate as raw materials and adopting a one-step method. At room temperature, the waste edible oil fatty amide is dissolved in acetone to obtain a 50 wt% waste edible oil fatty amide solution. Adding the waste edible oil fatty amide solution into toluene diisocyanate, and keeping the NCO/OH ratio at 1.2: 1, stirring dibutyltin dilaurate serving as a catalyst at 70 ℃ for 2 hours to reach a pourable viscosity to obtain a polyurethane prepolymer;
and step three, preparing modified polyurethane, namely dropwise adding the double-end amino-hydrocarbon-based silicone oil into the polyurethane prepolymer, keeping the molar ratio of the double-end amino-hydrocarbon-based silicone oil to the polyurethane prepolymer at 2:1, adjusting the viscosity of the system by using acetone, and continuously stirring and reacting for 3 hours at 55 ℃ to obtain the organic silicon modified polyurethane.
FIG. 2 is an infrared spectrum of waste edible oil fatty acid amide, wherein 3358cm-1Stretching vibration peak at OH, 2852 and 2920cm-1The absorption bands observed are due to CH respectively2And CH3Symmetric and asymmetric stretching of the groups, 1357cm-1And 1456cm-1Is represented by CH2Peak of flexural vibration, 1614cm-1The peak is C ═ O stretching vibration peak in amide group, and is 1207cm-1The presence of a peak at C-N stretching vibration, -N-C ═ O and-OH demonstrates the synthesis of waste edible oil fatty amides.
FIG. 3 is an infrared spectrum of a polyurethane prepolymer, in which 3340cm is used-1Is N-H stretching vibration peak, 1725cm-1Is the stretching vibration peak of carbamate C ═ O, 1600cm-1Is the stretching vibration peak of the benzene ring skeleton, 1230cm-1Is the C-O stretching vibration peak.
FIG. 4 is an infrared spectrum of 1075cm of the modified polyurethane-1The absorption peak became strong because of the overlapping of the Si-O-Si stretching vibration peak and the C-O-C stretching vibration peak, indicating that Si-O-Si was successfully introduced into the polyurethane main chain.
And step four, preparing the environment-friendly super-hydrophobic coating, dispersing silicon carbide particles with the particle size of 30 nanometers in an ethanol solution through ultrasonic treatment for 30min, then adding the double-end amino-hydrocarbon-based silicone oil, magnetically stirring for 4h at 70 ℃ to obtain a modified nano silicon carbide solution, and centrifugally washing and drying to obtain hydrophobic nano silicon carbide powder. Mixing organic silicon modified polyurethane and hydrophobic silicon carbide powder, wherein the mass ratio of the modified polyurethane to the hydrophobic silicon carbide powder is 4:1, spraying the mixture onto a substrate after magnetic stirring, and drying and curing to obtain the corresponding environment-friendly super-hydrophobic coating with high mechanical durability.
The contact angle of the superhydrophobic coating to a water drop was 163 ° measured using a DSA100 contact angle analyzer.
Fig. 5 is a scanning electron micrograph of the prepared superhydrophobic coating, and it can be found from the micrograph that spherical silicon carbide particles are uniformly distributed in a matrix to form a rough micro-nano surface.
The abrasion resistance of the superhydrophobic coating was evaluated by a sandpaper abrasion test, a weight of 200g was placed on the sample coated with the superhydrophobic coating, which was in contact with the sandpaper, and the sample was moved 20cm in the same direction for a total of 10 times. The relation between the contact angle and the abrasion times is shown in figure 6, and the contact angle of each group of liquid drops in figure 6 is larger than 150 degrees, which shows that the super-hydrophobic coating prepared by the invention has good mechanical durability.
Example 2:
firstly, putting sodium methoxide (0.007mol) and diethanolamine (0.32mol) into a three-neck round-bottom flask, turning on a heating switch and a magnetic stirring device, heating and stirring at 80 ℃ for 20 minutes, and then dropwise adding purified waste edible oil (0.1mol) within 60 minutes. After the purified waste edible oil is completely added, raising the reaction temperature to 120 ℃, and continuously stirring and reacting for 3 hours at the temperature to obtain waste edible oil fatty amide;
step two, preparing a polyurethane prepolymer, namely preparing the polyurethane prepolymer by using waste edible oil fatty amide and toluene diisocyanate as raw materials and adopting a one-step method. At room temperature, the waste edible oil fatty amide is dissolved in acetone to obtain a 50 wt% waste edible oil fatty amide solution. Adding the waste edible oil fatty amide solution into toluene diisocyanate, and keeping the NCO/OH ratio at 1.2: 1, stirring dibutyltin dilaurate serving as a catalyst at 70 ℃ for 2 hours to reach a pourable viscosity to obtain a polyurethane prepolymer;
and step three, preparing modified polyurethane, namely dropwise adding the double-end amino-hydrocarbon-based silicone oil into the polyurethane prepolymer, keeping the molar ratio of the double-end amino-hydrocarbon-based silicone oil to the polyurethane prepolymer at 2:1, adjusting the viscosity of the system by using acetone, and continuously stirring and reacting for 3 hours at 55 ℃ to obtain the organic silicon modified polyurethane.
And step four, preparing the environment-friendly super-hydrophobic coating, dispersing silicon carbide particles with the particle size of 30 nanometers in an ethanol solution through ultrasonic treatment for 30min, then adding the double-end amino-hydrocarbon-based silicone oil, magnetically stirring for 4h at 70 ℃ to obtain a modified nano silicon carbide solution, and centrifugally washing and drying to obtain hydrophobic nano silicon carbide powder. Mixing organic silicon modified polyurethane and hydrophobic silicon carbide powder, wherein the mass ratio of the modified polyurethane to the hydrophobic silicon carbide powder is 10:1, spraying the mixture onto a substrate after magnetic stirring, and drying and curing to obtain the corresponding environment-friendly super-hydrophobic coating.
The contact angle of the superhydrophobic coating to a water drop was measured to be 150 ° using a DSA100 contact angle analyzer.
Example 3:
firstly, putting sodium methoxide (0.007mol) and diethanolamine (0.32mol) into a three-neck round-bottom flask, turning on a heating switch and a magnetic stirring device, heating and stirring at 80 ℃ for 20 minutes, and then dropwise adding purified waste edible oil (0.1mol) within 60 minutes. After the purified waste edible oil is completely added, raising the reaction temperature to 120 ℃, and continuously stirring and reacting for 3 hours at the temperature to obtain waste edible oil fatty amide;
step two, preparing a polyurethane prepolymer, namely preparing the polyurethane prepolymer by using waste edible oil fatty amide and toluene diisocyanate as raw materials and adopting a one-step method. At room temperature, the waste edible oil fatty amide is dissolved in acetone to obtain a 50 wt% waste edible oil fatty amide solution. Adding the waste edible oil fatty amide solution into toluene diisocyanate, and keeping the NCO/OH ratio at 1.2: 1, stirring dibutyltin dilaurate serving as a catalyst at 70 ℃ for 2 hours to reach a pourable viscosity to obtain a polyurethane prepolymer;
and step three, preparing modified polyurethane, namely dropwise adding the double-end amino-hydrocarbon-based silicone oil into the polyurethane prepolymer, keeping the molar ratio of the double-end amino-hydrocarbon-based silicone oil to the polyurethane prepolymer at 2:1, adjusting the viscosity of the system by using acetone, and continuously stirring and reacting for 3 hours at 55 ℃ to obtain the organic silicon modified polyurethane.
And step four, preparing the environment-friendly super-hydrophobic coating, dispersing silicon carbide particles with the particle size of 30 nanometers in an ethanol solution through ultrasonic treatment for 30min, then adding the double-end amino-hydrocarbon-based silicone oil, magnetically stirring for 4h at 70 ℃ to obtain a modified nano silicon carbide solution, and centrifugally washing and drying to obtain hydrophobic nano silicon carbide powder. Mixing organic silicon modified polyurethane and hydrophobic silicon carbide powder, wherein the mass ratio of the modified polyurethane to the hydrophobic silicon carbide powder is 8:1, spraying the mixture onto a substrate after magnetic stirring, and drying and curing to obtain the corresponding environment-friendly super-hydrophobic coating.
The contact angle of the superhydrophobic coating to a water droplet was 155 ° measured using a DSA100 contact angle analyzer.
Example 4:
firstly, putting sodium methoxide (0.007mol) and diethanolamine (0.32mol) into a three-neck round-bottom flask, turning on a heating switch and a magnetic stirring device, heating and stirring at 80 ℃ for 20 minutes, and then dropwise adding purified waste edible oil (0.1mol) within 60 minutes. After the purified waste edible oil is completely added, raising the reaction temperature to 120 ℃, and continuously stirring and reacting for 3 hours at the temperature to obtain waste edible oil fatty amide;
step two, preparing a polyurethane prepolymer, namely preparing the polyurethane prepolymer by using waste edible oil fatty amide and toluene diisocyanate as raw materials and adopting a one-step method. At room temperature, the waste edible oil fatty amide is dissolved in acetone to obtain a 50 wt% waste edible oil fatty amide solution. Adding the waste edible oil fatty amide solution into toluene diisocyanate, and keeping the NCO/OH ratio at 1.2: 1, stirring dibutyltin dilaurate serving as a catalyst at 70 ℃ for 2 hours to reach a pourable viscosity to obtain a polyurethane prepolymer;
and step three, preparing modified polyurethane, namely dropwise adding the double-end amino-hydrocarbon-based silicone oil into the polyurethane prepolymer, keeping the molar ratio of the double-end amino-hydrocarbon-based silicone oil to the polyurethane prepolymer at 2:1, adjusting the viscosity of the system by using acetone, and continuously stirring and reacting for 3 hours at 55 ℃ to obtain the organic silicon modified polyurethane.
And step four, preparing the environment-friendly super-hydrophobic coating, dispersing silicon carbide particles with the particle size of 30 nanometers in an ethanol solution through ultrasonic treatment for 30min, then adding the double-end amino-hydrocarbon-based silicone oil, magnetically stirring for 4h at 70 ℃ to obtain a modified nano silicon carbide solution, and centrifugally washing and drying to obtain hydrophobic nano silicon carbide powder. Mixing organic silicon modified polyurethane and hydrophobic silicon carbide powder, wherein the mass ratio of the modified polyurethane to the hydrophobic silicon carbide powder is 6:1, spraying the mixture onto a substrate after magnetic stirring, and drying and curing to obtain the corresponding environment-friendly super-hydrophobic coating.
The contact angle of the superhydrophobic coating to a water drop was 159 ° using a DSA100 contact angle analyzer.
Example 5:
firstly, putting sodium methoxide (0.007mol) and diethanolamine (0.32mol) into a three-neck round-bottom flask, turning on a heating switch and a magnetic stirring device, heating and stirring at 80 ℃ for 20 minutes, and then dropwise adding purified waste edible oil (0.1mol) within 60 minutes. After the purified waste edible oil is completely added, raising the reaction temperature to 120 ℃, and continuously stirring and reacting for 3 hours at the temperature to obtain waste edible oil fatty amide;
step two, preparing a polyurethane prepolymer, namely preparing the polyurethane prepolymer by using waste edible oil fatty amide and toluene diisocyanate as raw materials and adopting a one-step method. At room temperature, the waste edible oil fatty amide is dissolved in acetone to obtain a 50 wt% waste edible oil fatty amide solution. Adding the waste edible oil fatty amide solution into toluene diisocyanate, and keeping the NCO/OH ratio at 1.2: 1, stirring dibutyltin dilaurate serving as a catalyst at 70 ℃ for 2 hours to reach a pourable viscosity to obtain a polyurethane prepolymer;
and step three, preparing modified polyurethane, namely dropwise adding the double-end amino-hydrocarbon-based silicone oil into the polyurethane prepolymer, keeping the molar ratio of the double-end amino-hydrocarbon-based silicone oil to the polyurethane prepolymer at 2:1, adjusting the viscosity of the system by using acetone, and continuously stirring and reacting for 3 hours at 55 ℃ to obtain the organic silicon modified polyurethane.
And step four, preparing the environment-friendly super-hydrophobic coating, dispersing silicon carbide particles with the particle size of 30 nanometers in an ethanol solution through ultrasonic treatment for 30min, then adding the double-end amino-hydrocarbon-based silicone oil, magnetically stirring for 4h at 70 ℃ to obtain a modified nano silicon carbide solution, and centrifugally washing and drying to obtain hydrophobic nano silicon carbide powder. Mixing organic silicon modified polyurethane and hydrophobic silicon carbide powder, wherein the mass ratio of the modified polyurethane to the hydrophobic silicon carbide powder is 2:1, spraying the mixture onto a substrate after magnetic stirring, and drying and curing to obtain the corresponding environment-friendly super-hydrophobic coating.
The contact angle of the superhydrophobic coating to a water drop was 161 ° measured using a DSA100 contact angle analyzer.
Comparative example 1:
compared with the example 1, in the fourth step, the hydrophobic treatment of the nano silicon carbide particles is omitted, except that the other steps are the same, the specific operation steps are as follows:
firstly, putting sodium methoxide (0.007mol) and diethanolamine (0.32mol) into a three-neck round-bottom flask, turning on a heating switch and a magnetic stirring device, heating and stirring at 80 ℃ for 20 minutes, and then dropwise adding purified waste edible oil (0.1mol) within 60 minutes. After the purified waste edible oil is completely added, raising the reaction temperature to 120 ℃, and continuously stirring and reacting for 3 hours at the temperature to obtain waste edible oil fatty amide;
step two, preparing a polyurethane prepolymer, namely preparing the polyurethane prepolymer by using waste edible oil fatty amide and toluene diisocyanate as raw materials and adopting a one-step method. At room temperature, the waste edible oil fatty amide is dissolved in acetone to obtain a 50 wt% waste edible oil fatty amide solution. Adding the waste edible oil fatty amide solution into toluene diisocyanate, and keeping the NCO/OH ratio at 1.2: 1, stirring dibutyltin dilaurate serving as a catalyst at 70 ℃ for 2 hours to reach a pourable viscosity to obtain a polyurethane prepolymer;
and step three, preparing modified polyurethane, namely dropwise adding the double-end amino-hydrocarbon-based silicone oil into the polyurethane prepolymer, keeping the molar ratio of the double-end amino-hydrocarbon-based silicone oil to the polyurethane prepolymer at 2:1, adjusting the viscosity of the system by using acetone, and continuously stirring and reacting for 3 hours at 55 ℃ to obtain the organic silicon modified polyurethane.
And step four, preparing a coating, namely mixing the organic silicon modified polyurethane with silicon carbide particles with the particle size of 30 nanometers, wherein the mass ratio of the modified polyurethane to the silicon carbide particles is 4:1, spraying the mixture onto a substrate after magnetic stirring, and drying and curing to obtain the corresponding coating.
The contact angle of the coating to a water drop was 117 ° as measured using a DSA100 contact angle analyzer.
Claims (2)
1. A preparation method of an environment-friendly super-hydrophobic coating with high mechanical durability is characterized by sequentially comprising the following steps:
a, preparing the waste edible oil fatty amide,
taking filtered and purified waste edible oil as a raw material, and synthesizing waste edible oil fatty amide through an amino decomposition reaction;
b, preparing a polyurethane prepolymer,
dissolving waste edible oil fatty amide in acetone at room temperature to obtain a 50 wt% waste edible oil fatty amide solution, adding the waste edible oil fatty amide solution into toluene diisocyanate, and stirring at a certain temperature by using dibutyltin dilaurate as a catalyst to obtain a polyurethane prepolymer, wherein the pourable viscosity is reached;
c, preparing the modified polyurethane by the method,
carrying out end capping on the polyurethane prepolymer by using double-end type amino-hydrocarbon silicone oil to prepare modified polyurethane;
d, preparing the environment-friendly super-hydrophobic coating,
hydrophobic silicon carbide powder is obtained by carrying out hydrophobic treatment on silicon carbide particles, then the modified polyurethane is mixed with the hydrophobic silicon carbide powder, is sprayed on a substrate after being magnetically stirred, and is dried and cured to obtain the silicon carbide powder;
in the step d, the hydrophobic treatment step is as follows: dispersing silicon carbide particles in an ethanol solution through ultrasonic treatment, then adding double-end type amino-hydrocarbon silicone oil, magnetically stirring at a certain temperature to obtain a modified nano silicon carbide solution, and centrifugally washing and drying to obtain hydrophobic silicon carbide powder;
the mass ratio of the hydrophobic silicon carbide powder to the modified polyurethane is 2-10: 1;
in the step a, the preparation steps of the waste edible oil fatty amide are as follows: firstly, putting sodium methoxide and diethanolamine into a reaction bottle, turning on a heating switch and a magnetic stirring device, heating and stirring at 80 ℃ for 20 minutes, then dropwise adding purified waste edible oil within 60 minutes, completely adding the purified waste edible oil, raising the reaction temperature to 120 ℃, and continuously stirring and reacting at the temperature for 3 hours to obtain the sodium methoxide, diethanolamine and waste edible oil, wherein the molar ratio of the sodium methoxide to the waste edible oil to the diethanolamine is 1:45: 15;
the molar ratio of the waste edible oil fatty amide to the toluene diisocyanate is 1:1.2, and the pourable viscosity can be reached after stirring for 2 hours at 70 ℃; the double-end amino alkyl silicone oil is synthesized by hydroxy polydimethylsiloxane and 3-aminopropyl triethoxysilane;
in the step c, dropwise adding the double-end amino-hydrocarbon-based silicone oil into the polyurethane prepolymer, adjusting the viscosity of the system by using acetone, and continuously stirring and reacting for 3 hours at 55 ℃ to obtain modified polyurethane; the molar ratio of the polyurethane prepolymer to the double-end amino-hydrocarbon silicone oil is 1: 2;
in the step d, the particle size of the silicon carbide particles is 30-100 nm, and the particle shape is spherical;
in the step d, the mass ratio of the silicon carbide particles to the ethanol solution to the double-end amino-hydrocarbon-based silicone oil is 2:3:10 in sequence, and the drying temperature is 130 ℃.
2. The method for preparing the environmentally-friendly superhydrophobic coating with high mechanical durability as claimed in claim 1, wherein: in the step of hydrophobic treatment, silicon carbide particles are dispersed in ethanol solution through ultrasonic treatment for 30min, then double-end type amino hydrocarbon silicone oil is added, and magnetic stirring is carried out for 4h at 70 ℃.
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