A giant POSS molecule-doped super-hydrophobic epoxy resin coating and its preparation method and application

Abstract

The application provides a super-hydrophobic epoxy resin coating doped with a giant POSS molecule and a preparation method and application thereof. The preparation method of the coating comprises the following steps: dissolving heptakis-trifluoropropylvinyl POSS, octamercapto propyl POSS, perfluorohexyl ethylene and a photoinitiator I into a solvent A, and performing a mercapto-olefin addition reaction under ultraviolet light to obtain a giant POSS molecule solution; dissolving an epoxy acrylate resin into a solvent B, adding a photoinitiator II to obtain an epoxy acrylate resin solution; uniformly mixing the giant POSS molecule solution and the epoxy acrylate resin solution, diluting to obtain a mixed solution; and coating the obtained mixed solution on a substrate and performing light curing to obtain the coating. The resin can form a coating on different substrates and has excellent hydrophobicity. The coating can be loaded on the surface of cotton fabric to endow the cotton fabric with super-hydrophobic properties and has a self-cleaning performance; and the coating can also be coated on the surface of copper to slow down the corrosion of copper.

Description

Technical Field

[0001] The invention relates to a giant POSS molecule-doped super-hydrophobic epoxy resin coating, a preparation method and application thereof, and belongs to the technical field of organosilicon surface modification. Background Art

[0002] In recent years, silsesquioxane materials have attracted widespread attention. Polyhedral oligomeric cage-type silsesquioxane (POSS) is a cubic multifunctional compound with the molecular formula [RSiO 1.5 ] n (R represents an organic functional group; n = 6, 8, 10, or 12, with n = 8 being the most common.) The POSS molecule consists of an inorganic core composed of silicon-oxygen-silicon bonds, which exhibit excellent thermal stability, rigidity, and radiation resistance. Furthermore, the silicon-oxygen-silicon bonds themselves have a low specific surface energy, allowing for easy self-assembly and the construction of coarse micro- and nanostructures. The POSS molecule is surrounded by various organic groups, and the substituents can be varied to suit the designer's needs, endowing the POSS with further functionality. Furthermore, the POSS molecule can be modified not only with organic groups but also with different types of POSS, forming giant molecules, increasing their size and potentially acquiring new properties. POSS is a highly hydrophobic additive that can effectively enhance the water repellency of a material's surface. However, POSS itself has a low surface energy and poor adhesion, making it prone to phase separation when used as an additive, which can reduce its lifespan. To address this phase separation issue, introducing modifiers into the coating via chemical bonding is a promising approach. Furthermore, substances containing a high number of hydrogen bonds can be used to enhance adhesion between the coating and the substrate. Commercially available, inexpensive epoxy acrylate (EA) resins can be used as adhesive substrates. Currently, they are the most widely used and fastest-polymerizing photocurable oligomer. They contain a large number of hydroxyl groups, which provide high adhesion. Epoxy acrylate resins can also be used as protective layers for metals to prevent corrosion. When epoxy acrylate resins are doped with low-surface-energy substances, their applications are further expanded. Chemical doping of POSS with EA exhibits excellent hydrophobic properties, enabling applications such as self-cleaning and corrosion protection.

[0003] So far, utilize POSS to carry out modification and receive people's attention gradually, but the POSS kind is relatively single, can not be fully utilized, and the research to giant branched POSS is even rarer, and use giant POSS as the research of hydrophobic modifier not yet reported.For this reason, propose the present invention. Summary of the Invention

[0004] Summary of the invention For the deficiencies in the prior art, the invention provides a kind of super-hydrophobic epoxy resin coating of giant POSS molecule doping and preparation method and application thereof. The present invention uses seven trifluoropropyl vinyl POSS, eight mercaptopropyl POSS and perfluorohexyl ethylene to prepare a kind of novel giant POSS molecule, and is doped in EA, obtains a kind of photocurable hydrophobic epoxy resin, the resin can form coating on different substrates, and has excellent hydrophobicity. The coating can be loaded onto the surface of cotton fabric to give cotton fabric super-hydrophobicity, with self-cleaning performance; The coating can also be applied to the surface of metallic copper, slows down the corrosion of copper, and has great potential in actual applications.

[0005] The technical solutions of the present invention are as follows:

[0006] A method for preparing a giant POSS molecule-doped super-hydrophobic epoxy resin coating comprises the following steps:

[0007] (1) dissolving heptatrifluoropropyl vinyl POSS (CF3-POSS), octamercaptopropyl POSS (SH-POSS), perfluorohexylethylene and photoinitiator I in solvent A, mixing and stirring uniformly, and performing a thiol addition reaction under ultraviolet light to obtain a giant POSS molecular solution;

[0008] (2) dissolving epoxy acrylate resin (EA) in solvent B and adding photoinitiator II to obtain an epoxy acrylate resin solution;

[0009] (3) The giant POSS molecule solution and the epoxy acrylate resin solution are mixed evenly and diluted to obtain a mixed solution; the obtained mixed solution is coated on a substrate and photocured to obtain a super-hydrophobic epoxy resin coating doped with the giant POSS molecules.

[0010] According to the present invention, preferably, the ratio of the total moles of heptatrifluoropropyl vinyl POSS (CF3-POSS) and perfluorohexylethylene to the mole number of octamercaptopropyl POSS (SH-POSS) in step (1) is 2-7:1, and more preferably 2-4:1; the molar ratio of heptatrifluoropropyl vinyl POSS (CF3-POSS) and perfluorohexylethylene is 1-6:1-6, and more preferably 1:1.

[0011] According to the present invention, the heptatrifluoropropyl vinyl POSS (CF3-POSS) and octamercaptopropyl POSS (SH-POSS) described in step (1) are prepared and synthesized according to the document Surface & Coatings Technology 457 (2023) 129285 and the document Advanced Functional Materials 2011, 21, 2960-2967, respectively, and have the structures described in the following formulas:

[0012]

[0013] According to the present application, preferably, the photoinitiator I in step (1) is 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 4-dimethylaminoethyl benzoate, benzophenone, 4-chlorobenzophenone, 4-methylbenzophenone or methyl o-benzoylbenzoate, and further preferably 2,2-dimethoxy-2-phenylacetophenone; the mass of the photoinitiator I is 1-2% of the total mass of heptafluoropropylvinyl POSS (CF3-POSS), octamercaptopropyl POSS (SH-POSS) and perfluorohexylethylene.

[0014] According to the present application, preferably, the solvent A in step (1) is tetrahydrofuran, dichloromethane, toluene, chloroform, methanol, ethanol, isopropanol or 1,2-dichloroethane, and further preferably tetrahydrofuran.

[0015] According to the present application, preferably, the light source of the ultraviolet light in step (1) is a 100W ultraviolet lamp, and the wavelength is 200-400nm.

[0016] According to the present application, preferably, the time of the thio-ene addition reaction in step (1) is 10-180min, and further preferably 50-70min.

[0017] According to the present application, preferably, the concentration of the giant POSS molecule in the solution of the giant POSS molecule in step (1) is 10-150mg / mL, and further preferably 45-50mg / mL; the mass of the giant POSS is calculated based on the total mass of heptafluoropropylvinyl POSS (CF3-POSS), octamercaptopropyl POSS (SH-POSS) and perfluorohexylethylene.

[0018] According to the present application, preferably, the solvent B in step (2) is the same as the solvent A in step (1).

[0019] According to the present application, preferably, the photoinitiator II in step (2) is 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 4-dimethylaminoethyl benzoate, benzophenone, 4-chlorobenzophenone, 4-methylbenzophenone or methyl o-benzoylbenzoate, and further preferably 2,2-dimethoxy-2-phenylacetophenone; the mass of the photoinitiator II is 1-2% of the mass of the epoxy acrylate resin.

[0020] According to the application, preferably, the concentration of the epoxy acrylate resin in the epoxy acrylate resin solution in step (2) is 100-400 mg / mL, and more preferably 200-300 mg / mL; the epoxy acrylate resin (EA) is prepared by esterification of an epoxy resin and acrylic acid or methacrylic acid, and the epoxy resin is bisphenol A type, bisphenol F type or phenolic type epoxy resin, and the epoxy acrylate resin is a common commercially available product.

[0021] According to the application, preferably, the mass of the giant POSS molecule in step (3) is 1-40% of the mass of the epoxy acrylate resin, and more preferably 5-20%, and even more preferably 10%; the mass of the giant POSS molecule is the total mass of heptafluoropropylvinyl POSS (CF3-POSS) and octamercaptan propyl POSS (SH-POSS).

[0022] According to the application, preferably, the dilution step in step (3) is dilution by adding solvent C to the system, and the solvent C is the same as solvent A; the concentration of the epoxy acrylate resin in the obtained mixed solution after dilution is 25-100 mg / mL, and more preferably 50-75 mg / mL.

[0023] According to the application, preferably, the substrate in step (3) is cotton fabric or copper sheet; the obtained mixed solution is coated on the substrate by a soaking treatment method; and more preferably, when the substrate is cotton fabric, the soaking treatment time is 10-30 min, and ultrasonic treatment is performed during the soaking process; and when the substrate is copper sheet, the soaking time is 5-20 s.

[0024] According to the application, preferably, the light curing conditions in step (3) are ultraviolet light irradiation for 10-40 min, and more preferably 20-30 min; and the wavelength of the ultraviolet light is 200-400 nm.

[0025] The application further provides a giant POSS molecule doped super-hydrophobic epoxy resin coating prepared by the above preparation method.

[0026] According to the application, the above giant POSS molecule doped super-hydrophobic epoxy resin coating is used in cotton fabric modification and copper corrosion prevention.

[0027] The technical features and advantages of the application are as follows:

[0028] 1, the present invention carries out sulfhydryl click chemistry reaction by seven trifluoropropyl vinyl POSS, eight mercaptopropyl POSS and perfluorohexyl ethylene and prepares a kind of novel giant POSS molecule, enriches the fluorine-containing giant POSS material for substrate surface modification;Then fluorine-containing giant POSS material and epoxy acrylate resin are coated on cotton fabric, due to hydrogen bond effect, the hydroxyl on cotton fabric can be strongly combined with epoxy acrylate resin, epoxy acrylate resin is firmly adhered to on substrate, ensures the structural stability of material;And giant POSS molecule is firmly connected on epoxy acrylate resin through sulfhydryl chemistry, finally obtains the super-hydrophobic epoxy coating of giant POSS molecule doping;Meanwhile, epoxy acrylate resin can firmly adhere to on copper sheet, and giant POSS molecule is firmly connected on epoxy acrylate resin through sulfhydryl chemistry, finally obtains the super-hydrophobic epoxy coating of giant POSS molecule doping, can effectively protect copper surface.Required reaction conditions of the present invention are gentle, simple, efficient, can be prepared in large quantities, and coating preparation process is concise and efficient.

[0029] 2. After the super-hydrophobic epoxy coating of giant POSS molecule doping of the present invention is applied to the cotton fabric surface, a stable super-hydrophobic surface is formed, and hydrophobic effect is obvious, and the water contact angle is more than 150 °, and there is good self-cleaning performance simultaneously; After coating is applied to the metal copper sheet surface, a hydrophobic coating is formed, and this coating can effectively protect the copper surface, slows down corrosion, and compared to other POSS molecules, anti-corrosion performance is more excellent simultaneously.

[0030] 3. The giant POSS molecule modified epoxy acrylate used in the present invention is then coated on the substrate, and the utilization rate of the POSS molecule is high. Simultaneously, the giant POSS molecule of the present invention has a low fluorine content and is easy to biodegrade. Adding a small amount of giant POSS molecules with a low fluorine content of the present invention can achieve the excellent hydrophobicity of cotton fabric and the anti-corrosion performance of copper sheet, with lower cost, more environmental advantages, and more excellent anti-corrosion performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 FT-IR spectra of the POSS molecules obtained in Example 1 and Comparative Examples 1-3.

[0032] Figure 2 This is a trend diagram of the change of water contact angle (WCA) and sliding angle (SA) of POSS-2-Fabric obtained in Comparative Example 1, POSS-4-Fabric obtained in Comparative Example 2, POSS-6-Fabric obtained in Comparative Example 3 and POSS-2F-Fabric obtained in Example 1 in Experimental Example 1.

[0033] Figure 3These are photos of different water droplets on the surface of POSS-2F-Fabric obtained in Example 1 of Experimental Example 1, from left to right: cola, tea, coffee, and methylene blue-dyed water.

[0034] Figure 4 This is a photograph of the POSS-2F-Fabric obtained in Example 1 in Experimental Example 2 immersed in a methylene blue solution.

[0035] Figure 5 This is a photo of coffee powder on the surface of the POSS-2F-Fabric obtained in Example 1 rinsed with methylene blue solution in Experimental Example 2.

[0036] Figure 6 It is the Tafel polarization curve diagram of POSS-2-Coating obtained in Comparative Example 1 in Experimental Example 3, POSS-4-Coating obtained in Comparative Example 2, POSS-6-Coating obtained in Comparative Example 3, and POSS-2F-Coating obtained in Example 1.

[0037] Figure 7 It is the Nyquist plot of POSS-2-Coating obtained in Comparative Example 1, POSS-4-Coating obtained in Comparative Example 2, POSS-6-Coating obtained in Comparative Example 3, and POSS-2F-Coating obtained in Example 1 in Experimental Example 3. DETAILED DESCRIPTION

[0038] The present invention will be further described below with reference to specific experimental examples and accompanying drawings, but the protection scope of the present invention is not limited thereto.

[0039] In the embodiment, the ultraviolet light is provided by a 100W ultraviolet lamp.

[0040] The epoxy acrylate resin used in the examples is available from Wenzhou Hengli New Materials Co., Ltd., model number HL-G100, and is obtained by reacting bisphenol A epoxy resin with acrylic acid.

[0041] Example 1

[0042] A method for preparing a giant POSS molecule-doped super-hydrophobic epoxy resin coating comprises the following steps:

[0043] (1) Heptatrifluoropropylvinyl POSS (752 mg, 0.670 mmol), octamercaptopropyl POSS (341 mg, 0.335 mmol), perfluorohexylethylene (232 mg, 0.670 mmol), 2,2-dimethoxy-2-phenylacetophenone (18 mg) and THF (26.5 mL) were added into an eggplant-shaped flask in sequence, stirred evenly and reacted under 365 nm ultraviolet light for 60 min to obtain a uniform and transparent giant POSS molecule (denoted as POSS-2F) solution with a concentration of 50 mg / mL.

[0044] (2) 1 g of epoxy acrylate resin (EA) was weighed and dissolved in 5 mL of THF, and 1% of the mass of the epoxy acrylate resin as a photoinitiator 2,2-dimethoxy-2-phenylacetophenone was added to obtain a 200 mg / mL epoxy acrylate resin solution; different volumes of the giant POSS molecule (POSS-2F) solution with a concentration of 50 mg / mL obtained in step (1) were added to the 200 mg / mL EA solution, respectively, so that the mass of POSS-2F was 1%, 3%, 5%, 7%, 10%, 20%, 30% and 40% of the mass of EA, respectively; then, THF was added to dilute the solution with EA as the base to obtain a mixed solution with an EA concentration of 50 mg / mL (POSS-2F was diluted simultaneously). The cotton fabric was immersed in the above mixed solution and ultrasonicated for 20 minutes. After being taken out, it was cured under 365nm ultraviolet light for 20 minutes to obtain a superhydrophobic epoxy resin coating doped with giant POSS molecules on the surface of the cotton fabric. The obtained modified superhydrophobic cotton fabric was recorded as POSS-2F-Fabric.

[0045] The giant POSS molecule obtained in this example has the following structure: Figure 1 shown.

[0046]

[0047] Example 2

[0048] A preparation method for a giant POSS molecule-doped super-hydrophobic epoxy resin coating is as described in Example 1, except that: in step (2), the cotton fabric is replaced with a copper sheet, the copper sheet is immersed in a solution for 10 seconds, taken out and cured under 365nm ultraviolet light for 20 minutes, and a giant POSS molecule-doped super-hydrophobic epoxy resin coating is obtained on the surface of the copper sheet, and the gained modified copper sheet is designated as POSS-2F-Coating.

[0049] Comparative Example 1

[0050] A method for preparing a POSS molecule-doped super-hydrophobic epoxy resin coating comprises the following steps:

[0051] (1) A 100 mL round bottom flask was charged with hepta (trifluoropropyl) ethenyl-POSS (752 mg, 0.670 mmol), octa (mercapto propyl) -POSS (341 mg, 0.335 mmol), 2,2-dimethoxy-2-phenylacetophenone (14.8 mg) and THF (22 mL). After stirring well, the mixture was irradiated with UV light at 365 nm for 60 min to give a uniform transparent POSS (denoted as POSS-2) solution with a concentration of 50 mg / mL.

[0052] (2) The modified superhydrophobic cotton fabric was prepared as described in step (2) of Example 1 and denoted as POSS-2-Fabric; the modified copper sheet was prepared as described in step (2) of Example 2 and denoted as POSS-2-Coating.

[0053] The POSS-2 obtained in this example has the structure shown below, and its infrared characterization is shown below. Figure 1

[0054]

[0055] Comparative Example 2

[0056] A method for preparing a POSS molecule-doped superhydrophobic epoxy resin coating was described in Comparative Example 1, except that in step (1), hepta (trifluoropropyl) ethenyl-POSS (1505 mg, 1.34 mmol), octa (mercapto propyl) -POSS (341 mg, 0.335 mmol), 2,2-dimethoxy-2-phenylacetophenone (25.1 mg) and THF (37 mL) were sequentially added to a 100 mL round bottom flask. After stirring well, the mixture was irradiated with UV light at 365 nm for 60 min to give a uniform transparent POSS (denoted as POSS-4) solution.

[0057] The modified superhydrophobic cotton fabric was denoted as POSS-4-Fabric; the modified copper sheet was denoted as POSS-4-Coating.

[0058] The POSS-4 obtained in this example has the structure shown below, and its infrared characterization is shown below. Figure 1

[0059]

[0060] Comparative Example 3

[0061] ​​A method for preparing a POSS molecule doped superhydrophobic epoxy resin coating was as described in Comparative Example 1, except that in step (1), octa-mercaptopropyl POSS (341 mg, 0.335 mmol), 2,2-dimethoxy-2-phenylacetophenone (35.3 mg) and THF (52 mL) were sequentially added into a flask, and after stirring uniformly, the reaction was carried out under 365 nm UV irradiation for 60 min to obtain a uniform transparent POSS solution (denoted as POSS-6).

[0062] The obtained modified superhydrophobic cotton fabric was denoted as POSS-6-Fabric; and the obtained modified copper sheet was denoted as POSS-6-Coating.

[0063] The POSS-6 obtained in the example had the structure shown below, and its infrared characterization was as shown in Figure 1 .

[0064]

[0065] Comparative Example 4

[0066] A method for preparing a POSS molecule doped superhydrophobic epoxy resin coating was as described in Example 1, except that in step (1), octa-mercaptopropyl POSS (114 mg, 0.112 mmol), DMPA (1.6 mg) and THF (12.5 mL) were sequentially added into a flask, and after stirring uniformly, the reaction was carried out under 365 nm UV irradiation for 60 min to obtain a uniform transparent POSS solution, however, using the POSS solution to prepare a coating (the mass of the POSS was 10% of the mass of the EA), the obtained coating had hydrophilicity.

[0067] Test Example 1

[0068] The liquid repellency of the samples obtained in Example 1 and Comparative Examples 1-3 was evaluated by the change of the water contact angle, and the results were as shown in Figure 2As shown. In the samples of all different POSS contents (referring to the mass percentage of POSS accounting for EA), when POSS content can approximately reach 10%, its water repellency almost no longer improves, which illustrates that the POSS molecules on the surface almost reach saturation, and therefore is best when POSS content is 10%. The contact angle values ​​of POSS-2F-Fabric obtained in Example 1 are all higher than the samples in the comparative example, and this is because a specific amount of perfluorohexylethylene is added in Example 1, and its hydrophobicity is stronger. The reason why the contact angle values ​​of POSS-4-Fabric and POSS-6-Fabric are lower is because there are too many cage-type molecules connected, which produce a shielding effect on reactive sulfhydryl groups, causing difficulty in cross-linking with EA, and hydrophobicity is lost. So POSS-2F-Fabric is the sample with the best performance. POSS-2F-Fabric can produce water repellency ( Figure 3 ).

[0069] Test Example 2

[0070] Self-cleaning application exploration:

[0071] Since the modified cotton fabric has good liquid repellency, it has potential application value in anti-fouling and self-cleaning. Figure 4 As shown, the modified cotton fabric (POSS content of 10%) obtained in Example 1 was immersed in sewage dyed with methylene blue dye, and then taken out. The surface of the cotton fabric was not contaminated and had anti-fouling ability; Figure 5 As shown, when coffee powder is sprinkled on the surface of cotton fabric, the pollutants can be removed by rinsing with water dyed with methylene blue, and it has a dual anti-fouling self-cleaning ability.

[0072] Test Example 3

[0073] Exploration of copper sheet anti-corrosion applications:

[0074] When the coating (POSS content is 10%) is applied to the copper sheet, the anti-corrosion effect of the modified copper sheet is greatly improved compared to the pure copper sheet. The anti-corrosion performance is analyzed using the Tafel polarization curve and electrochemical impedance spectroscopy of a three-electrode electrochemical workstation. The structure of the three-electrode system is as follows: the copper sheet and the modified copper sheet are working electrodes, Ag / AgCl is the reference electrode, the platinum sheet is the counter electrode, and the 3.5wt% NaCl solution is the electrolyte. The immersion area of ​​the working electrode is maintained at 1cm 2 The scanning speed of Tafel polarization curve is 10mV / s. The impedance frequency test range is between 1000000Hz and 0.01Hz. Figure 6As shown, when the pure copper sheet is covered by the coating, the corrosion current density decreases and the corrosion potential moves positively, in which the corrosion potential of POSS-2F-Coating moves positively the most, from -299 mV to -170 mV respectively, which indicates the effectiveness of the POSS functionalized silane coating in corrosion protection. Further, the corrosion protection performance is analyzed by using Nyquist diagram, as shown in Figure 7 As shown, the semicircle diameter of POSS-2F-Coating curve is the largest, which further indicates that the corrosion protection effect of POSS-2F-Coating is good.

[0075] The above embodiments are only the preferred embodiments of the present application, and are not intended to limit the present application.

Claims

1. A method for preparing a super-hydrophobic epoxy resin coating doped with giant POSS molecules comprises the following steps: (1) Dissolving heptatrifluoropropyl vinyl POSS, octamercaptopropyl POSS, perfluorohexylethylene and photoinitiator I in solvent A, mixing and stirring uniformly, and performing a thiol addition reaction under ultraviolet light to obtain a giant POSS molecular solution; the ratio of the total molar number of the heptatrifluoropropyl vinyl POSS and perfluorohexylethylene to the molar number of the octamercaptopropyl POSS is 2-4:1; the molar ratio of the heptatrifluoropropyl vinyl POSS to perfluorohexylethylene is 1:1; the concentration of the giant POSS molecules in the giant POSS molecular solution is 10-150 mg / mL; (2) dissolving epoxy acrylate resin in solvent B and adding photoinitiator II to obtain an epoxy acrylate resin solution; the concentration of epoxy acrylate resin in the epoxy acrylate resin solution is 100-400 mg / mL; (3) The giant POSS molecule solution and the epoxy acrylate resin solution are mixed evenly, and after dilution, a mixed solution is obtained; the obtained mixed solution is coated on a substrate, and photocured to obtain a super-hydrophobic epoxy resin coating doped with giant POSS molecules; the mass of the giant POSS molecules is 1-40% of the mass of the epoxy acrylate resin; the concentration of the epoxy acrylate resin in the diluted mixed solution is 25-100 mg / mL.

2. according to the preparation method of the super-hydrophobic epoxy coating of giant POSS molecule doping according to claim 1, it is characterized in that, The photoinitiator I in step (1) is 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, ethyl 4-dimethylaminobenzoate, benzophenone, 4-chlorobenzophenone, 4-methylbenzophenone or methyl o-benzoylbenzoate; the mass of the photoinitiator I is 1-2% of the total mass of heptatrifluoropropyl vinyl POSS, octamercaptopropyl POSS and perfluorohexylethylene.

3. according to the preparation method of the super-hydrophobic epoxy coating of giant POSS molecule doping according to claim 1, it is characterized in that, The solvent A in step (1) is tetrahydrofuran, dichloromethane, toluene, chloroform, methanol, ethanol, isopropanol or 1,2-dichloroethane; The ultraviolet light source is a 100W ultraviolet lamp with a wavelength of 200-400nm; The time of the thiol addition reaction is 10-180 minutes.

4. according to the preparation method of the super-hydrophobic epoxy coating of giant POSS molecule doping according to claim 1, it is characterized in that, The concentration of giant POSS molecules in the giant POSS molecule solution in step (1) is 45-50 mg / mL.

5. according to the preparation method of the super-hydrophobic epoxy coating of giant POSS molecule doping according to claim 1, it is characterized in that, The solvent B in step (2) is the same as the solvent A in step (1); The photoinitiator II is 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, ethyl 4-dimethylaminobenzoate, benzophenone, 4-chlorobenzophenone, 4-methylbenzophenone or methyl o-benzoylbenzoate; the mass of the photoinitiator II is 1-2% of the mass of the epoxy acrylic resin; The concentration of the epoxy acrylate resin in the epoxy acrylate resin solution is 200-300 mg / mL.

6. according to the preparation method of the super-hydrophobic epoxy coating of giant POSS molecule doping according to claim 1, it is characterized in that, The mass of the giant POSS molecule in step (3) is 5-20% of the mass of the epoxy acrylic resin; The dilution step in step (3) is to add solvent C to the system for dilution, wherein the solvent C is the same as solvent A; the concentration of the epoxy acrylate resin in the diluted mixed solution is 50-75 mg / mL.

7. according to the preparation method of the super-hydrophobic epoxy coating of giant POSS molecule doping according to claim 1, it is characterized in that, In step (3), the substrate is a cotton fabric or a copper sheet; the obtained mixed solution is coated on the substrate and soaked; when the substrate is a cotton fabric, the soaking time is 10-30 minutes, and ultrasonic treatment is performed during the soaking process; when the substrate is a copper sheet, the soaking time is 5-20 seconds; The conditions for the light curing are: ultraviolet light irradiation for 10-40 minutes; the ultraviolet light wavelength is 365 nm.

8. A giant POSS molecule-doped super-hydrophobic epoxy resin coating, characterized in that, The preparation method according to claim 1 is used for preparation.

9. the application of the super-hydrophobic epoxy coating of giant POSS molecule doping in cotton fabric modification and copper anticorrosion described in claim 8.

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