Flexible microstructure super-hydrophobic material and preparation method thereof
By spraying carboxylated carbon nanotube dispersion on the substrate material and forming a low surface energy layer, the problem of poor durability of existing superhydrophobic materials is solved, and a high-durability superhydrophobic surface is achieved, and excellent superhydrophobic performance is maintained.
Patent Information
- Application Number
- CN202510271308.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-06-13
- Filing Date
- 2025-03-08
- Publication Date
- 2025-05-30
AI Technical Summary
The superhydrophobic materials prepared by existing spraying methods have poor durability and the coating is prone to fall off, resulting in damage to superhydrophobicity.
Spray the carboxylated carbon nanotube dispersion on the substrate material to form a nanoscale velvety nanostructure, and form a low-surface energy layer on the surface, which improves the adhesion ability of the superhydrophobic surface through chemical bond connections between the components.
The durability and fastness of superhydrophobic materials is significantly improved, and the superhydrophobic properties are maintained. Even after multiple bends, the static water contact angle above 150° and the rolling angle less than 10° can be maintained.
Smart Images
Figure CN120059265A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of superhydrophobic materials, and particularly relates to a flexible microstructured superhydrophobic material and a preparation method thereof. Background Art
[0002] Superhydrophobic materials have many excellent properties, such as self-cleaning, corrosion prevention, and reduction of flow resistance, etc. These properties are due to their superhydrophobic surfaces. The so-called superhydrophobic surface refers to a class of material surfaces with a contact angle with water greater than 150° and a rolling angle less than 10°. Through research, it is found that there are two key factors for superhydrophobic surfaces: one is to have a micro-nano composite rough structure of a certain scale, and the other is to be modified with low-surface-energy substances on the basis of a certain roughness to reduce the surface energy of the material. Thus, it can be seen that preparing a superhydrophobic surface usually requires increasing the surface roughness and reducing the surface energy.
[0003] Currently, there are various methods for constructing superhydrophobic surfaces, such as chemical vapor deposition, chemical etching, sol-gel method, electrospinning method, layer-by-layer self-assembly method, spraying method, etc. Among them, in the spraying method, a superhydrophobic material is dissolved in a suitable solvent and sprayed onto the surface of an object by spraying to prepare a superhydrophobic coating. Currently, the superhydrophobic materials obtained by a simple spraying method usually have the defect of poor durability, and the surface structure is prone to fall off during application, resulting in the destruction of their superhydrophobicity. Therefore, how to obtain a superhydrophobic material with excellent durability is a research and development direction with market value. Summary of the Invention
[0004] The purpose of the present invention is to solve the problem of poor durability of superhydrophobic materials prepared by the spraying method and easy shedding of the coating, and to provide a flexible microstructured superhydrophobic material and a preparation method thereof. This method sprays a carboxylated carbon nanotube dispersion liquid on a substrate material, and the carboxylated carbon nanotubes form a nanoscale villous nanostructure covering the substrate material. Aminopropyl-terminated polydimethylsiloxane forms a low-surface-energy layer on the surface, constructs a superhydrophobic surface, and improves the adhesion ability of the superhydrophobic surface on the substrate material through chemical bond connection between components, thereby improving the durability and fastness of the superhydrophobic material.
[0005] To achieve the above purpose, the technical solution adopted by the present invention is as follows:
[0006] A preparation method of a flexible microstructured superhydrophobic material, the method comprising the following steps:
[0007] Step 1: Place the substrate material in a plasma cleaner for treatment;
[0008] Step 2: Immerse the substrate material treated in Step 1 in an inositol 1,5-diphosphate solution for 30 - 60 min, and set aside;
[0009] Step 3: Disperse the carboxylated carbon nanotubes in the amino-propyl-terminated polydimethylsiloxane. After heating to 40-50°C, add dihydroxyacetone to prepare a carbon nanotube dispersion.
[0010] Step 4: Take out the substrate material soaked in Step 2, spray the carbon nanotube dispersion prepared in Step 3 on its surface, and dry it.
[0011] Step 5: Heat-treat the product dried in Step 4 under normal pressure at a temperature of 110-120°C for 1-1.5 h, and cool it to obtain a flexible microstructured superhydrophobic material.
[0012] Further, in Step 1, the substrate material is one of polyester fiber cloth, silicone, PI film, or PET film.
[0013] Further, in Step 1, oxygen plasma treatment is used, with a treatment time of 5-10 min, a power of 100-200 W, a gas pressure of 0.1-0.3 Pa, a gas flow rate of 20-50 sccm, and the distance between the substrate material and the plasma source is 5-10 cm.
[0014] Further, in Step 2, in the inositol 1,5-diphosphate solution, the volume ratio of inositol 1,5-diphosphate to pure water is 1:70-90.
[0015] Further, in Step 3, the dispersion method uses an ultrasonic disperser for ultrasonic dispersion, with an ultrasonic power of 100-150 W, an ultrasonic treatment time of 30-60 min, an ultrasonic frequency of 20-40 kHz, the dispersion temperature is controlled at 40-50°C, the dispersion medium is ethanol or deionized water, ethanol or deionized water is used to dissolve and uniformly disperse the carboxylated carbon nanotubes, amino-propyl-terminated polydimethylsiloxane, and dihydroxyacetone, the stirring speed is 200-500 rpm, the diameter of the ultrasonic probe is 5-10 mm, and the intermittent ultrasonic mode is adopted, with the ultrasonic working for 5 minutes and resting for 2 minutes, and the cycle is carried out until the dispersion is completed.
[0016] Further, in Step 3, the mass-volume ratio of the carboxylated carbon nanotubes, amino-propyl-terminated polydimethylsiloxane, dihydroxyacetone to the dispersion medium is 1 g:70-80 g:0.01-0.015 g:50-100 mL.
[0017] Further, in Step 3, the diameter of the carboxylated carbon nanotubes is 10-200 nm.
[0018] Further, in step 3, a catalyst is also added. The catalyst is dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC); the mass ratio of the catalyst to the carboxyl group is 1:1. The catalyst is very effective in promoting the activation of carboxyl groups, making them more reactive towards the nucleophilic attack of amino groups and promoting the formation of amide bonds.
[0019] Further, in step 4, the spraying pressure is 0.3 - 0.4 MPa and the thickness is 0.5 - 1 mm; the drying temperature is 40 - 100 °C and the time is 2 - 4 h.
[0020] A flexible microstructured superhydrophobic material is prepared by using the preparation method described in any one of the above.
[0021] Compared with the prior art, the excellent features of the present invention are as follows:
[0022] 1. For the flexible microstructured superhydrophobic material of the present invention, the substrate material is first subjected to oxygen plasma impact so that the surface of the substrate material has hydroxyl groups, and then immersed in inositol 1,5-diphosphate solution, so that inositol 1,5-diphosphate acts on the hydroxyl groups in the substrate material to fix inositol 1,5-diphosphate on the surface of the substrate material; moreover, carboxylated carbon nanotubes are dispersed in aminopropyl-terminated polydimethylsiloxane, and the carboxyl groups on the carboxylated carbon nanotubes can condense with the amino groups in aminopropyl-terminated polydimethylsiloxane under the action of a catalyst, so that aminopropyl-terminated polydimethylsiloxane is tightly connected around the carboxylated carbon nanotubes. Finally, the dispersion is sprayed on the substrate material by spraying, and the amino groups of aminopropyl-terminated polydimethylsiloxane can condense with the phosphate groups of inositol 1,5-diphosphate, so that when the carboxylated carbon nanotubes are deposited on the surface of the flexible substrate, the aminopropyl-terminated polydimethylsiloxane connected around them is fixed on the substrate by chemical bonding with inositol 1,5-diphosphate; thus, it can be seen that the present invention tightly combines the structures by multiple chemical bonds, improving the durability and fastness of the superhydrophobic material.
[0023] 2. For the flexible microstructured superhydrophobic material of the present invention, carbon nanotubes are used to form a nano-scale villous nanostructure deposited on the surface of the substrate material, and at the same time, aminopropyl-terminated polydimethylsiloxane has a low surface energy, thus constructing a superhydrophobic surface.
[0024] 3. The flexible microstructured superhydrophobic material of the present invention uses aminopropyl-terminated polydimethylsiloxane as a flexible polymer to enhance the structural strength, bringing excellent flexibility to the material, being able to withstand various deformations and recover its original shape at room temperature, and being able to be better applied to real life.
[0025] 4. Due to van der Waals forces and strong intermolecular interactions, carbon nanotubes tend to aggregate in solution. Dihydroxymethyl acetone stabilizes the dispersion of carbon nanotubes by preventing them from aggregating, ensuring that they remain evenly dispersed in the solution. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 It is a schematic diagram of the process principle of the present invention;
[0027] Figure 2 This is a comparison diagram of the static water contact angle of the surface of the bent part of Example 4 of the present invention and Comparative Example 4, which are tested to restore flatness after 0 bending, 50 bending, 100 bending, and 200 bending (no white marks should appear after slight bending). DETAILED DESCRIPTION
[0028] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0029] In order to facilitate those skilled in the art to implement the present invention, some of the reagents used in the embodiments and comparative examples are now described: base material: PI film, Suri Electric; inositol 1,5-diphosphate: Beijing Bailingwei; carboxylated carbon nanotubes: carboxylated multi-walled carbon nanotubes, diameter 100nm, Guangdong Innovation Materials; aminopropyl-terminated polydimethylsiloxane: Shandong Xiya Chemical; polydimethylsiloxane: Shandong Xiya Chemical; dihydroxymethyl acetone: Shanghai Darui Fine Chemicals.
[0030] Example 1
[0031] A flexible microstructured super-hydrophobic material, the preparation steps comprising:
[0032] Step 1, placing the PI film in an oxygen plasma cleaning machine for treatment; oxygen plasma treatment is used, the treatment time is 10 min, the power is 100 W, the gas pressure is 0.3 Pa, the gas flow rate is 20 sccm, and the distance between the substrate material and the plasma source is 5 cm;
[0033] Step 2, prepare an inositol 1,5-bisphosphate solution according to a volume ratio of inositol 1,5-bisphosphate to pure water of 1:70, then cut the substrate material treated in step 1 into 3×3 cm pieces, immerse it in the inositol 1,5-bisphosphate solution for 30 minutes, and set aside;
[0034] Step 3: Disperse carboxylated carbon nanotubes in amino-propyl terminated polydimethylsiloxane, and add the catalyst dicyclohexylcarbodiimide (DCC). Use ultrasonic dispersion. At room temperature, the ultrasonic power is 100 W and the ultrasonic treatment time is 30 min. Then, after heating to 40 °C, add dihydroxymethylacetone to prepare a carbon nanotube dispersion. Among them, the mass ratio of carboxylated carbon nanotubes: amino-propyl terminated polydimethylsiloxane: dihydroxymethylacetone is 1:70:0.01, and the mass ratio of the catalyst to the carboxyl group is 1:1. The dispersion medium is ethanol, and the volume of the dispersion medium is 50 mL. Ethanol is used to dissolve and uniformly disperse 1 g of carboxylated carbon nanotubes, 70 g of amino-propyl terminated polydimethylsiloxane, and 0.01 g of dihydroxymethylacetone. The stirring speed is 250 rpm, the diameter of the ultrasonic probe is 10 mm, and the intermittent ultrasonic mode is adopted, with ultrasonic working for 5 minutes and resting for 2 minutes. The carboxylated carbon nanotubes are 50 nm.
[0035] Step 4: Take out the substrate material soaked in Step 2, and spray the carbon nanotube dispersion prepared in Step 3 on its surface. The spraying pressure is 0.3 MPa, the spraying thickness is 0.5 mm, and dry at 40 °C for 2 h.
[0036] Step 5: Heat-treat the product dried in Step 4 under normal pressure at a temperature of 110 °C for 1 h, and obtain a flexible microstructured superhydrophobic material after cooling.
[0037] Example 2
[0038] A flexible microstructured superhydrophobic material, the preparation steps include:
[0039] Step 1: Place the PI film in an oxygen plasma cleaner for treatment. Use oxygen plasma treatment, the treatment time is 5 min, the power is 200 W, the air pressure is 0.1 a, the gas flow rate is 50 sccm, and the distance between the substrate material and the plasma source is 10 cm.
[0040] Step 2: Prepare an inositol 1,5-diphosphate solution according to the volume ratio of inositol 1,5-diphosphate to pure water of 1:90. Then cut the substrate material treated in Step 1 into 3×3 cm, and soak it in the inositol 1,5-diphosphate solution for 60 min for standby.
[0041] Step 3: Disperse carboxylated carbon nanotubes in amino propyl terminated polydimethylsiloxane, and add the catalyst 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC). Use ultrasonic dispersion. At room temperature, the ultrasonic power is 150 W and the ultrasonic treatment time is 60 min. Then, after heating to 50 °C, add dihydroxyacetone to prepare a carbon nanotube dispersion. Among them, the mass ratio of carboxylated carbon nanotubes: amino propyl terminated polydimethylsiloxane: dihydroxyacetone is 1:80:0.015, and the mass ratio of the catalyst to the carboxyl group is 1:1. The dispersion medium is deionized water, and the volume of the dispersion medium is 100 mL. The deionized water is used to dissolve and uniformly disperse 1 g of carboxylated carbon nanotubes, 80 g of amino propyl terminated polydimethylsiloxane, and 0.015 g of dihydroxyacetone. The stirring speed is 200 rpm, the diameter of the ultrasonic probe is 8 mm, and the intermittent ultrasonic mode is adopted. The ultrasonic works for 5 minutes and rests for 2 minutes. The carboxylated carbon nanotubes are 100 nm.
[0042] Step 4: Take out the substrate material soaked in Step 2, and spray the carbon nanotube dispersion prepared in Step 3 on its surface. The spraying pressure is 0.3 MPa, the spraying thickness is 0.5 mm, and dry at 40 °C for 2 h.
[0043] Step 5: Heat-treat the product dried in Step 4 under normal pressure at a temperature of 110 °C for 1 h, and obtain a flexible microstructured superhydrophobic material after cooling.
[0044] Example 3
[0045] A flexible microstructured superhydrophobic material, the preparation steps include:
[0046] Step 1: Place the PI film in an oxygen plasma cleaner for treatment; use oxygen plasma treatment, the treatment time is 5-7 min, the power is 150 W, the air pressure is 0.15 Pa, the gas flow rate is 35 sccm, and the distance between the substrate material and the plasma source is 7 cm.
[0047] Step 2: Prepare an inositol 1,5-diphosphate solution according to the volume ratio of inositol 1,5-diphosphate to pure water of 1:80. Then cut the substrate material treated in Step 1 into 3×3 cm, soak it in the inositol 1,5-diphosphate solution for 40 min, and set aside.
[0048] Step 3: Disperse carboxylated carbon nanotubes in aminopropyl-terminated polydimethylsiloxane, and add the catalyst dicyclohexylcarbodiimide (DCC). Use ultrasonic dispersion. At room temperature, the ultrasonic power is 130 W and the ultrasonic treatment time is 50 min. Then, heat up to 45 °C and add dihydroxyacetone to prepare a carbon nanotube dispersion. Among them, the mass ratio of carboxylated carbon nanotubes: aminopropyl-terminated polydimethylsiloxane: dihydroxyacetone is 1:75:0.011, and the mass ratio of the catalyst to the carboxyl group is 1:1. The dispersion medium is deionized water, and the volume of the dispersion medium is 50 mL. The deionized water is used to dissolve and uniformly disperse 1 g of carboxylated carbon nanotubes, 75 g of aminopropyl-terminated polydimethylsiloxane, and 0.011 g of dihydroxyacetone. The stirring speed is 500 rpm, the diameter of the ultrasonic probe is 5 mm, and the intermittent ultrasonic mode is adopted, with ultrasonic working for 5 minutes and resting for 2 minutes. The carboxylated carbon nanotubes are 120 nm.
[0049] Step 4: Take out the substrate material soaked in Step 2, and spray the carbon nanotube dispersion prepared in Step 3 on its surface. The spraying pressure is 0.3 MPa, the spraying thickness is 0.5 mm, and dry at 40 °C for 2 h.
[0050] Step 5: Heat-treat the product dried in Step 4 under normal pressure at a temperature of 110 °C for 1 h, and obtain a flexible microstructured superhydrophobic material after cooling.
[0051] Example 4
[0052] A flexible microstructured superhydrophobic material, the preparation steps include:
[0053] Step 1: Place the PI film in an oxygen plasma cleaner for treatment; use oxygen plasma treatment, the treatment time is 5 min, the power is 100 W, the air pressure is 0.3 Pa, the gas flow rate is 20 sccm, and the distance between the substrate material and the plasma source is 5 cm.
[0054] Step 2: Prepare an inositol 1,5-diphosphate solution according to the volume ratio of inositol 1,5-diphosphate to pure water of 1:80. Then cut the substrate material treated in Step 1 into 3×3 cm, soak it in the inositol 1,5-diphosphate solution for 50 min, and set aside.
[0055] Step 3: Disperse carboxylated carbon nanotubes in amino-propyl terminated polydimethylsiloxane, and add catalyst 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC). Use ultrasonic dispersion. At room temperature, the ultrasonic power is 140 W and the ultrasonic treatment time is 50 min. Then, after heating to 40 °C, add dihydroxyacetone to prepare a carbon nanotube dispersion. Among them, the mass ratio of carboxylated carbon nanotubes: amino-propyl terminated polydimethylsiloxane: dihydroxyacetone is 1:77:0.015, and the mass ratio of the catalyst to carboxyl is 1:1. The dispersion medium is ethanol, and the volume of the dispersion medium is 100 mL. Ethanol is used to dissolve and uniformly disperse 1 g of carboxylated carbon nanotubes, 77 g of amino-propyl terminated polydimethylsiloxane, and 0.015 g of dihydroxyacetone. The stirring speed is 450 rpm, the diameter of the ultrasonic probe is 7 mm, and the intermittent ultrasonic mode is adopted. The ultrasonic works for 5 minutes and rests for 2 minutes. The carboxylated carbon nanotubes are 120 nm.
[0056] Step 4: Take out the substrate material soaked in Step 2, and spray the carbon nanotube dispersion prepared in Step 3 on its surface. The spraying pressure is 0.3 MPa, the spraying thickness is 0.5 mm, and dry at 40 °C for 2 h.
[0057] Step 5: Heat-treat the product dried in Step 4 at normal pressure and a temperature of 110 °C for 1 h, and obtain a flexible microstructured superhydrophobic material after cooling.
[0058] Comparative Example 1
[0059] Commercially available PI film 3×3 cm.
[0060] Comparative Example 2
[0061] A kind of flexible microstructured hydrophobic material, the preparation steps include:
[0062] Step 1: Prepare an inositol 1,5-diphosphate solution according to the volume ratio of inositol 1,5-diphosphate to pure water of 1:90. Then cut an untreated substrate material of 3×3 cm and soak it in the inositol 1,5-diphosphate solution for 60 min for standby.
[0063] Step 2: Disperse carboxylated carbon nanotubes in amino-propyl terminated polydimethylsiloxane, and use ultrasonic dispersion. At room temperature, the ultrasonic power is 150 W and the ultrasonic treatment time is 60 min. Then, after heating to 50 °C, add dihydroxyacetone to prepare a carbon nanotube dispersion. Among them, the carboxylated carbon nanotubes are 1 g, the amino-propyl terminated polydimethylsiloxane is 80 g, and the mass of dihydroxyacetone is 0.015 g. Use 100 mL of deionized water for dispersion.
[0064] Step 3: Take out the substrate material after soaking in Step 1, spray the carbon nanotube dispersion prepared in Step 2 on its surface, with a spraying pressure of 0.4 MPa and a spraying thickness of 0.5 mm, and dry at 100 °C for 4 h;
[0065] Step 4: Heat-treat the product after drying in Step 3 under normal pressure at a temperature of 120 °C for 1.5 h, and obtain a flexible microstructured hydrophobic material after cooling.
[0066] Comparative Example 3
[0067] A flexible microstructured hydrophobic material, the preparation steps include:
[0068] Step 1: Cut the substrate material processed in Step 1 of Example 1 into 3×3 cm;
[0069] Step 2: Disperse carboxylated carbon nanotubes in aminopropyl-terminated polydimethylsiloxane, and perform ultrasonic dispersion. At room temperature, the ultrasonic power is 150 W and the ultrasonic treatment time is 60 min; then heat up to 50 °C and add dihydroxyacetone to prepare a carbon nanotube dispersion; among them, the carboxylated carbon nanotubes are 1 g, the aminopropyl-terminated polydimethylsiloxane is 80 g, the mass of dihydroxyacetone is 0.015 g, and 100 mL of deionized water is used for dispersion;
[0070] Step 3: Spray the carbon nanotube dispersion prepared in Step 2 on the surface of the substrate material in Step 1, with a spraying pressure of 0.4 MPa and a spraying thickness of 0.5 mm, and dry at 100 °C for 4 h;
[0071] Step 4: Heat-treat the product after drying in Step 3 under normal pressure at a temperature of 120 °C for 1.5 h, and obtain a flexible microstructured hydrophobic material after cooling.
[0072] Comparative Example 4
[0073] A flexible microstructured hydrophobic material, the preparation steps include:
[0074] Step 1: Prepare an inositol 1,5-diphosphate solution according to the volume ratio of inositol 1,5-diphosphate to pure water of 1:90. Then cut the substrate material processed in Step 1 of Example 1 into 3×3 cm and soak it in the inositol 1,5-diphosphate solution for 60 min for standby;
[0075] Step 2: Disperse carboxylated carbon nanotubes in polydimethylsiloxane, and perform ultrasonic dispersion. At room temperature, the ultrasonic power is 150 W and the ultrasonic treatment time is 60 min; among them, the mass of carboxylated carbon nanotubes is 1 g, the mass of polydimethylsiloxane is 80 g, and 100 mL of deionized water is used for dispersion;
[0076] Step 3: Take out the substrate material after soaking in Step 1, spray the carbon nanotube dispersion prepared in Step 2 on its surface, with a spraying pressure of 0.4 MPa and a spraying thickness of 0.5 mm, and dry at 100 °C for 4 h;
[0077] Step 4: Heat-treat the product dried in Step 3 under normal pressure at a temperature of 120 °C for 1.5 h, and obtain a flexible microstructured hydrophobic material after cooling.
[0078] Hydrophobic performance test: For the films obtained in the above examples and comparative examples, measure the surface static water contact angle and rolling angle at the bending part after 0 bending, 50 bendings, 100 bendings, and 200 bendings and then restoring to flat (no white marks should appear for slight bending), with reference to the standard GB / T 30693-2014.
[0079] The test results are as follows in the table:
[0080]
[0081]
[0082] It can be seen from the above table that for the flexible microstructured superhydrophobic materials prepared in Examples 1-4 of the present invention, the surface static water contact angle remains above 150° after 200 bendings, and the rolling angle is less than 10°, indicating that it still maintains superhydrophobic performance. This proves that the flexible microstructured superhydrophobic material of the present invention has excellent durability.
[0083] Comparative Example 1 uses a commercially available PI film, which is untreated and does not have superhydrophobic performance.
[0084] Compared with the operation steps of the examples, the substrate material in Comparative Example 2 is not treated with oxygen plasma, resulting in poor adhesion of the superhydrophobic surface layer to the substrate material. After 100 bendings, the superhydrophobic surface is damaged.
[0085] Compared with the operation steps of the examples, Comparative Example 3 lacks the process of soaking the substrate material in inositol 1,5-diphosphate solution. Inositol 1,5-diphosphate plays a key role in connecting the upper and lower layers. Due to the lack, after 100 bendings, the superhydrophobic surface has been damaged.
[0086] Compared with the operation steps of the examples, in Comparative Example 4, polydimethylsiloxane is used instead of aminopropyl-terminated polydimethylsiloxane, resulting in a weakened bonding force between the carboxylated carbon nanotubes and the substrate material. After 100 bendings, the superhydrophobic surface is damaged.
[0087] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A method for preparing a flexible microstructured super-hydrophobic material, characterized in that: The method comprises the following steps: Step 1, placing the substrate material in a plasma cleaning machine for treatment; Step 2: Soak the substrate material treated in step 1 in an inositol 1,5-diphosphate solution for 30 to 60 minutes for later use; Step 3, dispersing the carboxylated carbon nanotubes in aminopropyl-terminated polydimethylsiloxane, heating to 40-50° C. and then adding dihydroxymethyl acetone to prepare a carbon nanotube dispersion; Step 4, taking out the base material soaked in step 2, spraying the carbon nanotube dispersion prepared in step 3 on its surface, and drying; Step 5: heat-treating the product obtained after drying in step 4 at normal pressure and temperature of 110-120° C. for 1-1.5 h, and obtaining a flexible microstructure super-hydrophobic material after cooling.
2. The method for preparing a flexible microstructured super-hydrophobic material according to claim 1, wherein: In step 1, the base material is one of polyester fiber cloth, silicone, PI film or PET film.
3. The method for preparing the flexible microstructure super-hydrophobic material according to claim 1, characterized in that: In step 1, oxygen plasma treatment is adopted, the treatment time is 5 to 10 minutes, the power is 100 to 200 W, the gas pressure is 0.1 to 0.3 Pa, the gas flow rate is 20 to 50 sccm, and the distance between the substrate material and the plasma source is 5 to 10 cm.
4. The method for preparing the flexible microstructure super-hydrophobic material according to claim 1, characterized in that: In step 2, in the inositol 1,5-bisphosphate solution, the volume ratio of inositol 1,5-bisphosphate to pure water is 1:70-90.
5. The method for preparing the flexible microstructure super-hydrophobic material according to claim 1, characterized in that: In step 3, the dispersion method adopts an ultrasonic disperser for ultrasonic dispersion, the ultrasonic power is 100-150W, the ultrasonic treatment time is 30-60min, the ultrasonic frequency is 20-40kHz, the dispersion temperature is controlled at 40-50°C, the dispersion medium is ethanol or deionized water, ethanol or deionized water is used to dissolve and evenly disperse the carboxylated carbon nanotubes, aminopropyl-terminated polydimethylsiloxane, and dihydroxymethyl acetone, the stirring speed is 200-500rpm, the ultrasonic probe diameter is 5-10mm, and the intermittent ultrasonic mode is adopted. The ultrasonic work is 5 minutes, the rest is 2 minutes, and the cycle is carried out until the dispersion is completed.
6. The method for preparing the flexible microstructure super-hydrophobic material according to claim 5, characterized in that: In step 3, the mass volume ratio of carboxylated carbon nanotubes, aminopropyl-terminated polydimethylsiloxane, dihydroxymethyl acetone and dispersion medium is 1 g: 70-80 g: 0.01-0.015 g: 50-100 mL.
7. The method for preparing the flexible microstructure super-hydrophobic material according to claim 1, characterized in that: In step 3, the diameter of the carboxylated carbon nanotubes is 10 to 200 nm.
8. The method for preparing the flexible microstructure super-hydrophobic material according to claim 1, characterized in that: In step 3, a catalyst is also added, and the catalyst is dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC); the mass ratio of the catalyst to the carboxyl group is 1:
1.
9. The method for preparing the flexible microstructure super-hydrophobic material according to claim 1, characterized in that: In step 4, the spraying pressure is 0.3-0.4 MPa, the thickness is 0.5-1 mm; the drying temperature is 40-100° C., and the drying time is 2-4 h.
10. A flexible microstructured super-hydrophobic material, characterized in that: The compound is prepared by any one of the preparation methods 1 to 9.