Preparation method of underwater self-repairing super-hydrophilic drag reduction and antibacterial scale and paraffin inhibition coating
The superhydrophilic coating prepared by the layer-by-layer spraying method solves the problem of easy damage to the coating in the underwater environment, and achieves self-healing, antibacterial and drag-reducing effects, thereby improving the stability and service life of the coating.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- NORTHEAST GASOLINEEUM UNIV
- Filing Date
- 2025-03-11
- Publication Date
- 2026-04-24
AI Technical Summary
Existing superhydrophilic coatings are easily damaged in underwater environments, have weakened self-healing capabilities, insufficient antibacterial properties, and poor drag reduction effects, making it impossible to maintain stable performance in extreme environments.
A layer-by-layer spraying method is adopted, which utilizes the ring-opening reaction of epoxy resin and curing agent to combine antibacterial substances and hydrophilic polymers to form a heat-induced self-healing coating. Stable cross-linking is formed through the chemical reaction of epoxy groups with amine groups and amine groups with aldehyde groups, which increases the physicochemical stability of the coating. Aldehyde-based carbon quantum dots and glycidyltrimethylammonium chloride are introduced to enhance hydrophilicity and antibacterial properties.
It achieves self-healing function of coating in underwater environment, improves antifouling and drag reduction performance, enhances surface wear resistance and stability, reduces friction coefficient, has antibacterial properties, inhibits mineral crystal adhesion, and extends coating service life.
Smart Images
Figure CN119931463B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of functional coating technology, and particularly relates to a method for preparing an underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating. Background Technology
[0002] Superhydrophilic surfaces, as unique surfaces with extreme wettability, have broad application prospects in fields such as antifouling, drag reduction, scale inhibition, wax prevention, and separation of oily wastewater. The process of preparing coatings using a single hydrophilic polymer through a one-step spraying method is widely used due to its simplicity, cost reduction, and time-saving advantages. However, in real-world working environments, organic coatings are easily damaged, leading to loss of effectiveness and even the loss of protection for the substrate. This increases repair costs and may create safety hazards. Furthermore, bacterial metabolism produces acidic or alkaline substances that can chemically react with superhydrophilic surfaces, causing surface performance degradation. For example, some materials are prone to dissolution or decomposition in acidic environments, weakening their superhydrophilicity and stability. Fluid resistance also significantly impacts equipment operating efficiency and economy; excessive frictional resistance can even cause coating cracking, creating safety hazards. Imparting antibacterial and self-healing capabilities to coatings is an effective method because it can repair damage under specific conditions, restore the coating's functionality and protective effects, and reduce bacterial adhesion, allowing it to maintain stability during practical applications. However, when the self-healing coating is in extreme underwater environments, the reversible dynamic bonds are easily affected by strong acids / bases and metal ions. This weakens its self-healing ability, making it unable to effectively repair damaged surface structures and severely impacting drag reduction. Furthermore, antibacterial substances cannot effectively and stably bond with the coating, thus losing its antibacterial properties.
[0003] Therefore, it is essential to develop a novel, superhydrophilic, multifunctional coating that can be stably repaired in extreme underwater environments using a layer-by-layer spraying process. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention proposes a method for preparing an underwater self-healing, superhydrophilic, impedance-reducing, anti-scaling, and anti-wax coating.
[0005] To achieve the above objectives, the present invention provides the following technical solution:
[0006] One of the technical solutions of this invention:
[0007] A method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating includes the following steps:
[0008] (1) Dissolve oily epoxy resin, octadecylamine and curing agent in an organic solvent and prepare epoxy resin-ODA substrate coating by coating method;
[0009] (2) A layer of polyethyleneimine (PEI) / epoxypropyltrimethylammonium chloride (EPTAC) emulsion is sprayed onto the epoxy resin-ODA substrate coating to obtain coating 1;
[0010] (3) Spray a layer of aldehyde-based carbon quantum dot ethanol solution onto the coating 1 to obtain coating 2;
[0011] (4) Repeat steps (2) and (3), and finally cure the obtained coating to prepare the underwater self-healing superhydrophilic resistance-reducing bacteria scale-inhibiting and wax-preventing coating.
[0012] Beneficial Effects: The method described in this invention enables the preparation of a thermally induced self-healing epoxy resin substrate through the ring-opening reaction of epoxy resin and curing agent without the use of surfactants. Then, an antibacterial substance and a hydrophilic polymer are mixed to prepare a stable emulsion for spraying, followed by the spraying of an aldehyde-based carbon quantum dot ethanol solution. This is repeated in a cycle to ultimately obtain an underwater self-healing superhydrophilic impedance-reducing antibacterial surface. This method of preparing an underwater self-healing superhydrophilic impedance-reducing antibacterial scale-inhibiting and anti-wax coating using a layer-by-layer spraying approach has the advantages of simplicity, speed, and large-scale production capability, solving the problems of complex and demanding preparation processes for underwater self-healing superhydrophilic impedance-reducing antibacterial scale-inhibiting and anti-wax coatings.
[0013] Optionally, the oily epoxy resin is a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.
[0014] Furthermore, the bisphenol A type epoxy resin is selected from at least one of E42 epoxy resin or E44 epoxy resin; the bisphenol F type epoxy resin is F51 epoxy resin.
[0015] Optionally, the curing agent is a cashew nut phenol modified curing agent.
[0016] Optionally, the ratio of the oily epoxy resin, octadecylamine, curing agent and anhydrous ethanol is 1g:0.9g:0.25-1g:2mL.
[0017] Optionally, the mass ratio of polyethyleneimine (PEI) to glycidyltrimethylammonium chloride (EPTAC) in the polyethyleneimine (PEI) / epoxypropyltrimethylammonium chloride (EPTAC) emulsion is 1:(0.9-2).
[0018] Optionally, the concentration of the aldehyde-based carbon quantum dot ethanol solution is 10-70 g / L.
[0019] Furthermore, the preparation process of the aldehyde-based carbon quantum dots in the ethanol solution is as follows:
[0020] Aldehyde compounds were mixed with anhydrous ethanol in a sealed polytetrafluoroethylene bottle, and then heated, cooled, and centrifuged sequentially to obtain CQDs. -CHO .
[0021] Furthermore, the volume ratio of the aldehyde compound to anhydrous ethanol is 1:2;
[0022] Furthermore, the aldehyde compound is glutaraldehyde.
[0023] Furthermore, the conditions during the heating process are: heating at 150°C for 4 hours.
[0024] Optionally, the number of times steps (2) and (3) are repeated is 3-5 times;
[0025] The curing conditions are as follows: curing at 60-120℃ for 2-8 hours.
[0026] Optionally, the temperature during the spraying process in step (1) is 90°C; the temperature during the spraying processes in steps (2) and (3) is 60°C.
[0027] The second technical solution of this invention:
[0028] An underwater self-healing, superhydrophilic, impedance-reducing, antibacterial, scale-inhibiting, and anti-wax coating is prepared by the above-mentioned preparation method.
[0029] Current superhydrophilic surfaces inevitably suffer microscopic or macroscopic damage during processing and use. Cracks formed on the surface or inside are difficult to repair and can fatally impact the performance of superhydrophilic surfaces (material strength, superhydrophilicity, and drag reduction). Furthermore, coatings prepared from single hydrophilic polymers still require further improvement in terms of wear resistance, oil and wax resistance, scale prevention, and drag reduction. Therefore, compared with existing technologies, this invention has the following advantages and technical effects:
[0030] This invention uses an epoxy resin layer with thermally induced self-healing function as the adhesive layer. A stable emulsion formed by PEI and EPTAC, followed by aldehyde-based carbon quantum dots, is then sequentially sprayed onto the epoxy resin layer surface. The chemical reactions between epoxy and amine groups, and between amine and aldehyde groups, form a stable cross-linking, improving the physicochemical stability of the coating underwater. This results in a super-hydrophilic, drag-reducing, and antifouling surface with underwater self-healing capabilities. The coating of this invention uses ODA (Oxygen Demand Acid) to control the cross-linking density of the epoxy resin, improving the underwater repair and stability of the coating. Layer-by-layer spraying of hydrophilic polymers and aldehyde-based carbon quantum dots creates a hydrophilic antifouling and drag-reducing layer, thereby achieving stronger antifouling and drag-reducing performance. Furthermore, the chemical bonds formed by the reactions of epoxy and amine groups, and amine and aldehyde groups, create a stable network structure, improving surface abrasion resistance and underwater stability. Simultaneously, the thickness of the hydrophilic antifouling and drag-reducing layer is controlled by adjusting the number of spray layers, optimizing the antifouling and drag-reducing performance of the hydrophilic layer. By leveraging its enhanced drag-reduction properties and stable hydrophilic polymer network structure, the surface wear resistance is further improved. Furthermore, the aldehyde residues on the carbon dot surface undergo a Schiff base reaction with the primary amine of PEI to generate dynamic imine bonds, exhibiting self-healing properties. Combined with the self-healing properties of the epoxy resin layer, both the hydrophilic and epoxy resin layers of the coating possess self-healing capabilities, significantly extending the service life of the coating surface. When the coating is immersed in water, the three-dimensional cross-linked network formed by PEI and aldehyde carbon dots undergoes a certain degree of water absorption and swelling, forming a lubricating layer of a certain thickness, similar to fish skin mucus, which greatly reduces the coefficient of friction, thereby improving the drag-reduction effect. The hydrophilicity of the coating is enhanced by introducing epipropyltrimethylammonium chloride (EPTAC). Moreover, EPTAC is a quaternary ammonium salt with low toxicity, low irritation, and excellent antibacterial properties. The introduction of EPTAC endows the coating with bactericidal characteristics. Simultaneously, due to the positive charge effect of the quaternary ammonium salt, it not only forms a dense positive electric field effect in the hydrophilic layer but also forms positively charged molecular brushes on the coating surface. This design not only utilizes the positive electric field effect to repel the adsorption and deposition of metal ions on the surface, but also employs the superhydrophilicity of the molecular brush structure and the assisted movement of fluids to inhibit the adhesion of mineral crystals to the coating surface, achieving a dual enhancement of the coating's anti-fouling performance. The introduction of epipropyltrimethylammonium chloride (EPTAC) enhances the surface's hydrophilicity, allowing water droplets to spread more quickly and improving the surface's oleophobicity. Combined with the dynamic molecular brush structure on the surface, this synergistic effect improves the coating's anti-wax properties.
[0031] Furthermore, when the surface hydrophilic layer consists solely of PEI, all surface properties, including hydrophilicity, anti-waxing, anti-fouling, and drag reduction, decrease. Surface wear resistance also declines, and there is no antibacterial property, making it unable to inhibit bacterial growth on the surface. This is detrimental to the coating's antifouling and drag reduction properties. Similarly, when the hydrophilic layer lacks glycidyltrimethylammonium chloride, the surface hydrophilicity decreases, water droplet spreading time is prolonged, and antibacterial properties are also absent. When PEI, glycidyltrimethylammonium chloride, and aldehyde-based carbon quantum dots are mixed simultaneously, a gel quickly forms, making further spraying impossible. Therefore, it cannot be used to prepare superhydrophilic coatings. Thus, a layer-by-layer spraying process is essential. Attached Figure Description
[0032] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:
[0033] Figure 1 The image shows the self-healing effect of the underwater self-healing superhydrophilic impedance-reducing antibacterial scale-inhibiting and anti-wax coating prepared in Example 1 of the present invention.
[0034] Figure 2 The underwater friction coefficient reduction diagrams are shown for the original coating E44 / ODA prepared in Comparative Example 1, the coating prepared in Comparative Example 3, and the underwater self-healing superhydrophilic resistance-reducing bacterial scale-inhibiting and wax-preventing coating prepared in Example 1 of this invention.
[0035] Figure 3 These are images showing the antibacterial effects of the underwater self-healing superhydrophilic resistance-reducing antibacterial, scale-inhibiting, and wax-preventing coating prepared in Example 1 of this invention and the coating prepared in Comparative Example 1.
[0036] Figure 4 The coatings prepared in Comparative Examples 1 and 3, and the underwater self-healing superhydrophilic impedance-reducing anti-scaling and anti-wax coating prepared in Example 1 of this invention are shown in the scale inhibition effect diagram.
[0037] Figure 5 The coatings prepared in Comparative Examples 1 and 3, and the underwater self-healing superhydrophilic impedance-reducing antibacterial scale-inhibiting and anti-wax coating prepared in Example 1 of the present invention are shown in the anti-wax effect diagram.
[0038] Figure 6These are images showing the corrosion resistance of commercial epoxy coatings and the underwater self-healing superhydrophilic impedance-reducing antibacterial scale-inhibiting and anti-wax coatings prepared in Example 1 of this invention to acids, alkalis, and seawater. Specifically, a is an image of three pieces of the underwater self-healing superhydrophilic impedance-reducing antibacterial scale-inhibiting and anti-wax coatings prepared in Example 1; b is an image of three pieces of commercial epoxy coatings; c is an image of the underwater self-healing superhydrophilic impedance-reducing antibacterial scale-inhibiting and anti-wax coatings prepared in Example 1 after immersion in 2M hydrochloric acid, 2M sodium hydroxide, and seawater for 2 hours; d is an image of the commercial epoxy coating after immersion in 2M hydrochloric acid, 2M sodium hydroxide, and seawater for 2 hours; e is an image of the underwater self-healing superhydrophilic impedance-reducing antibacterial scale-inhibiting and anti-wax coatings prepared in Example 1 after immersion in 2M hydrochloric acid, 2M sodium hydroxide, and seawater for 8 hours; and f is an image of the commercial epoxy coating after immersion in 2M hydrochloric acid, 2M sodium hydroxide, and seawater for 8 hours.
[0039] Figure 7 This is a diagram showing the wear resistance effect of the underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating prepared in Example 1 of the present invention. Detailed Implementation
[0040] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.
[0041] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0042] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0043] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.
[0044] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.
[0045] This invention discloses a method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating, which includes the following steps:
[0046] Step 1: Glutaraldehyde CQDs -CHO Preparation of ethanol solution
[0047] Glutaraldehyde and anhydrous ethanol were mixed in a sealed polytetrafluoroethylene (PTFE) bottle at a volume ratio of 1:2 and heated in an oven at 150°C for 4 hours. After the reaction was complete, the PTFE bottle was cooled, and the resulting brown solid was redispersed in acetone and chloroform, and centrifuged to remove carbon aggregates. This process was repeated three times for each solvent, and the mixture was evaporated under reduced pressure to obtain the brown solid. The CQDs were then... -CHO When added dropwise to anhydrous ethanol, glutaraldehyde CQDs are obtained. -CHO Ethanol solution, in which CQDs -CHO The concentration in anhydrous ethanol is 10-70 g / L.
[0048] Step 2: Preparation of underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating
[0049] (1) First, the epoxy resin, octadecylamine and cashew phenol modified curing agent are uniformly mixed in ethyl acetate, and then coated on the glass slide substrate. The solvent is placed on the heating table to fully evaporate until there are no bubbles on the coating surface, thus obtaining the epoxy resin-ODA substrate coating.
[0050] (2) Polyethyleneimine (PEI) and glycidyltrimethylammonium chloride (EPTAC) were dissolved together in anhydrous ethanol to obtain a PEI / EPTAC emulsion. After the temperature of the heating table was reduced to 60°C, the pre-prepared PEI / EPTAC emulsion was sprayed onto the epoxy resin-ODA substrate coating to obtain coating 1.
[0051] (3) Continue to spray another layer of CQDs prepared in step one onto coating 1. -CHO Coating 2 was obtained; the steps of preparing coating 1 and coating 2 were repeated multiple times, and the coating was cured at 60°C for 8 hours to obtain the coating; finally, the obtained coating was washed with deionized water and dried to prepare an underwater self-healing superhydrophilic impedance-reducing antibacterial scale-inhibiting and antiwax coating.
[0052] The glutaraldehyde CQDs used in the following embodiments of the present invention -CHO All of them were prepared through step one above.
[0053] Unless otherwise specified, "room temperature" in this invention refers to 20-30℃. The spraying process involves using a spray gun; antibacterial properties are assessed by observing the growth state of *E. coli*; scale inhibition is measured by testing the scale content of the coating in a saturated CaCO3 solution; wax resistance is measured by testing the wax content of the coating in waxy crude oil; and coating durability is assessed by its resistance to corrosion from acids, alkalis, and seawater.
[0054] All raw materials used in this invention were purchased commercially. The cashew phenol-modified amine curing agent used in the following examples was purchased from Xuzhou Zhongyan Technology Co., Ltd., model ZY7505; the epoxy curing agent was purchased from Jianglai Biotechnology Co., Ltd., model DF1228H.
[0055] The technical solution of the present invention will be further illustrated by the following embodiments.
[0056] Example 1
[0057] A method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating includes the following steps:
[0058] (1) Mix 1g of E44 epoxy resin, 0.9g of octadecylamine and 0.25g of cashew phenol modified amine curing agent evenly in 2mL of ethyl acetate to obtain a mixed solution. Then, coat the mixed solution onto a glass slide substrate and place it on a 90℃ heating table to allow the solvent to fully evaporate until there are no bubbles on the coating surface to obtain an E44 / ODA coating.
[0059] (2) Weigh 1g of polyethyleneimine (PEI) and 0.9g of glycidyltrimethylammonium chloride (EPTAC) and dissolve them in 10mL of anhydrous ethanol to obtain a PEI / EPTAC emulsion; after the temperature of the heating table is reduced to 60℃, the PEI / EPTAC emulsion is sprayed onto the E44 / ODA coating to obtain coating 1.
[0060] (3) Maintain a temperature of 60°C, and then spray a layer of CQDs onto coating 1. -CHO (500 mg, dissolved in 10 mL ethanol), to obtain coating 2;
[0061] (4) Repeat the steps of spraying coating 1 and coating 2 5 times, and cure the obtained coating at 60°C for 8 hours. Finally, wash the obtained coating with deionized water and dry it to obtain an underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating.
[0062] Comparative Example 1 (Original Coating E44 / ODA)
[0063] The preparation process of the original coating is as follows:
[0064] 1g of E44 epoxy resin, 0.9g of octadecylamine and 0.25g of cashew phenol modified amine curing agent were uniformly mixed in 2mL of ethyl acetate to obtain a mixed solution. The mixed solution was then coated onto a glass slide substrate and placed on a 90℃ heating stage to allow the solvent to fully evaporate until there were no bubbles on the coating surface, thus obtaining the original coating E44 / ODA.
[0065] Comparative Example 2 (E44 / ODA / PEI / EPTAC coating)
[0066] The preparation process of the E44 / ODA / PEI / EPTAC coating is as follows:
[0067] (1) Mix 1g of E44 epoxy resin, 0.9g of octadecylamine and 0.25g of cashew phenol modified amine curing agent evenly in 2mL of ethyl acetate to obtain a mixed solution. Then, coat the mixed solution onto a glass slide substrate and place it on a 90℃ heating table to allow the solvent to fully evaporate until there are no bubbles on the coating surface to obtain an E44 / ODA coating.
[0068] (2) Weigh 1g of polyethyleneimine (PEI) and dissolve it in 10mL of anhydrous ethanol to obtain PEI / EPTAC emulsion; after the temperature of the heating table is reduced to 60℃, spray the PEI / EPTAC emulsion onto the E44 / ODA coating to obtain the coating E44 / ODA / PEI / EPTAC.
[0069] Comparative Example 3
[0070] A method for preparing an underwater self-healing superhydrophilic coating includes the following steps:
[0071] (1) Mix 1g of E44 epoxy resin, 0.9g of octadecylamine and 0.25g of cashew phenol modified amine curing agent evenly in 2mL of ethyl acetate to obtain a mixed solution. Then, apply the mixed solution to a glass slide substrate and place it on a 90℃ heating table to allow the solvent to evaporate fully until there are no bubbles on the coating surface, thus obtaining an E44 / ODA substrate coating.
[0072] (2) Weigh 1g of polyethyleneimine (PEI) and 0.9g of glycidyltrimethylammonium chloride (EPTAC) and dissolve them in 10mL of anhydrous ethanol to obtain a PEI / EPTAC emulsion; after the temperature of the heating table is reduced to 60℃, the PEI / EPTAC emulsion is sprayed onto the E44 / ODA substrate coating to obtain coating 1.
[0073] (3) Spray a layer of CQDs onto coating 1. -CHO (500 mg, dissolved in 10 mL ethanol), to obtain coating 2;
[0074] The obtained composite coating was cured at 60°C for 8 hours. Finally, the coating was washed with deionized water and dried to obtain an underwater self-healing superhydrophilic coating.
[0075] Comparative Example 4
[0076] Commercial epoxy coating, purchased from Dongguan Heima Chemical Co., Ltd.; Model: BH644 waterborne epoxy resin.
[0077] Figure 1 The image shows the self-healing effect of the underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating prepared in Example 1 of the present invention. As can be seen from the image, the surface of the coating prepared in Example 1 is repaired in about 1 minute.
[0078] Figure 2 The figures show the underwater friction coefficient reduction of the original E44 / ODA coating prepared in Comparative Example 1, the coating prepared in Comparative Example 3, and the underwater self-healing superhydrophilic drag-reducing, anti-drag, anti-scaling, and anti-wax coating prepared in Example 1 of this invention. As can be seen from the figures, the surface of the coating prepared in Example 1 has a lower underwater friction coefficient than the original coating (only one layer of E44 / ODA sprayed) and Comparative Example 3 (only one layer of spraying), proving that the coating prepared in Example 1 has an excellent drag reduction effect.
[0079] Figure 3 These are images showing the antibacterial effects of the underwater self-healing superhydrophilic antimicrobial, scale-inhibiting, and wax-resistant coating prepared in Example 1 of this invention, and the coating prepared in Comparative Example 1. Specifically, the images show the original coating E44 / ODA (Comparative Example 1) and the coating prepared in Example 1 before and after immersion in E. coli solution (E. coli concentration of 512 Ug / mL) for 36 hours. As can be seen from the images, no bacterial colonies were formed on the surface of the coating prepared in Example 1, indicating that the coating prepared in Example 1 can effectively inhibit the growth of E. coli.
[0080] Figure 4 The figures show the scale inhibition effects of the original coating prepared in Comparative Example 1, the coating prepared in Comparative Example 3, and the underwater self-healing superhydrophilic anti-resistance, antibacterial, scale-inhibiting, and anti-wax coating prepared in Example 1 of this invention. As can be seen from the figures, the amount of scale on the surface of the coating prepared in Example 1 is less than that of the coatings in Comparative Example 1 and Comparative Example 3 (mass of saturated calcium carbonate), proving that the surface coating prepared in Example 1 of this invention has a good scale inhibition effect.
[0081] Figure 5 The figures show the anti-wax effect of the original coating prepared in Comparative Example 1, the coating prepared in Comparative Example 3, and the underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating prepared in Example 1 of this invention. As can be seen from the figures, the amount of wax deposition is less than that of the original coating prepared in Comparative Example 1 and the coating prepared in Comparative Example 3, which proves that the surface coating prepared in Example 1 of this invention has a good anti-wax effect.
[0082] Figure 6 The figures show the corrosion resistance of the commercially available epoxy coating purchased in Example 4 and the underwater self-healing superhydrophilic resistance-reducing antibacterial, scale-inhibiting, and anti-wax coating prepared in Example 1 of this invention against acids, alkalis, and seawater. As can be seen from the figures, when the immersion time increases from 2 hours to 8 hours, the corrosion resistance of E44 / ODA / PEI / EPTAC / CQDs decreases. -CHO The changes in the appearance of the coating were negligible. In contrast, the commercial epoxy coating separated from the substrate after immersion in 2M hydrochloric acid for 2 hours, indicating poor chemical stability. Furthermore, the commercial epoxy coating also showed significant peeling after immersion in 2M NaOH solution and seawater for 8 hours. However, E44 / ODA / PEI / EPTAC / CQDs -CHO The coating still maintains its intact appearance after immersion for 8 hours, demonstrating good resistance to acid, alkali and seawater corrosion.
[0083] Figure 7 This is a wear resistance effect diagram of the underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating prepared in Example 1 of the present invention. As can be seen from the diagram, the wear resistance of the coating is significantly improved under E44 / ODA / PEI / EPTAC / CQDs. -CHO A weight of 200g was applied to the coating, and a friction cycle test was conducted on 800-grit sandpaper. Each friction cycle consisted of 10cm of friction before and after the coating. After 100 friction cycles, the underwater oil droplet contact angle of the coating was greater than 150°, maintaining its superoleophobic properties underwater. This indicates that the PEI was not completely worn away, demonstrating excellent wear resistance and good mechanical stability.
[0084] Example 2
[0085] A method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating includes the following steps:
[0086] (1) Mix 1g of F51 epoxy resin, 0.9g of octadecylamine and 1g of epoxy curing agent evenly in 2mL of ethyl acetate, then coat the mixed solution onto a glass slide substrate, place it on a 90℃ heating table to allow the solvent to evaporate fully until there are no bubbles on the coating surface, and obtain the F51-ODA coating.
[0087] (2) Weigh 1g of polyethyleneimine (PEI) and 0.9g of glycidyltrimethylammonium chloride (EPTAC) and dissolve them in 10mL of anhydrous ethanol to obtain a PEI / EPTAC emulsion. After the temperature of the heating table is reduced to 60℃, the PEI / EPTAC emulsion is sprayed onto the F51-ODA coating to obtain coating 1.
[0088] (3) Then, a layer of the prepared CQDs is sprayed onto coating 1. -CHO (500 mg, dissolved in 10 mL ethanol), to obtain coating 2;
[0089] (4) Repeat the steps of spraying coating 1 and coating 2 four times, and cure the resulting coating at 60°C for 8 hours. Finally, wash the resulting coating with deionized water and dry it to obtain an underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating.
[0090] Example 3
[0091] A method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating includes the following steps:
[0092] (1) Mix 1g of E42 epoxy resin, 0.9g of octadecylamine and 0.25g of epoxy resin curing agent evenly in 2mL of ethyl acetate, then coat it on a glass slide substrate, place it on a 90℃ heating table to allow the solvent to evaporate fully until there are no bubbles on the coating surface, and prepare a bisphenol A-ODA coating.
[0093] (2) Weigh 0.5g polyethyleneimine (PEI) and 0.5g glycidyltrimethylammonium chloride (EPTAC) and dissolve them in 10mL of anhydrous ethanol. After the temperature of the heating table is reduced to 60℃, the PEI / EPTAC emulsion is sprayed onto the bisphenol A-ODA coating to obtain coating 1.
[0094] (3) Then, a layer of the prepared CQDs is sprayed onto coating 1. -CHO (500 mg, dissolved in 10 mL ethanol), to obtain coating 2;
[0095] (4) Repeat the steps of spraying coating 1 and coating 2 5 times, and cure the obtained coating at 80°C for 8 hours. Finally, wash the obtained coating with deionized water and dry it to obtain an underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating.
[0096] Example 4
[0097] A method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating includes the following steps:
[0098] (1) Mix 1g of E42 epoxy resin, 0.9g of octadecylamine and 0.25g of epoxy resin curing agent evenly in 2mL of ethyl acetate, then coat it on a glass slide substrate, place it on a 90℃ heating table to allow the solvent to evaporate fully until there are no bubbles on the coating surface, and prepare E42-ODA coating.
[0099] (2) Weigh 0.5g polyethyleneimine (PEI) and 1g glycidyltrimethylammonium chloride (EPTAC) and dissolve them in 10mL of anhydrous ethanol. After the temperature of the heating table is reduced to 60℃, the PEI / EPTAC emulsion is sprayed onto the E42-ODA coating to obtain coating 1.
[0100] (3) Then, a layer of the prepared CQDs is sprayed onto coating 1. -CHO (0.1g, dissolved in 10mL ethanol) to obtain coating 2;
[0101] (4) Repeat the steps of spraying coating 1 and coating 2 four times, and cure the obtained coating at 90°C for 8 hours. Finally, wash the obtained coating with deionized water and dry it to obtain an underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating.
[0102] Example 5
[0103] A method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating includes the following steps:
[0104] (1) Mix 1g F51 epoxy resin, 0.9g octadecylamine and 0.25g epoxy resin curing agent evenly in 2mL ethyl acetate, then coat it on a glass slide substrate, place it on a 90℃ heating table to allow the solvent to fully evaporate until there are no bubbles on the coating surface, and prepare bisphenol F-ODA coating.
[0105] (2) Weigh 1g of polyethyleneimine (PEI) and 0.9g of glycidyltrimethylammonium chloride (EPTAC) and dissolve them in 10mL of anhydrous ethanol. After the temperature of the heating table is reduced to 60℃, the PEI / EPTAC emulsion is sprayed onto the bisphenol F-ODA coating to obtain coating 1.
[0106] (3) Then, a layer of the prepared CQDs is sprayed onto coating 1. -CHO (700 mg, dissolved in 10 mL ethanol), to obtain coating 2;
[0107] (4) Repeat the steps of spraying coating 1 and coating 2 four times, and cure the resulting coating at 120°C for 8 hours. Finally, wash the resulting coating with deionized water and dry it to obtain an underwater self-healing superhydrophilic resistance-reducing antibacterial scale-inhibiting and anti-wax coating.
[0108] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.
Claims
1. A method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating, characterized in that, Includes the following steps: (1) Dissolve oily epoxy resin, octadecylamine and curing agent in an organic solvent and prepare epoxy resin-ODA substrate coating by coating method; (2) Spray a layer of polyethyleneimine / epoxypropyltrimethylammonium chloride emulsion onto the epoxy resin-ODA substrate coating to obtain coating 1; (3) Spray a layer of aldehyde-based carbon quantum dot ethanol solution onto the coating 1 to obtain coating 2; (4) Repeat steps (2) and (3), and finally cure the obtained coating to prepare the underwater self-healing superhydrophilic resistance-reducing bacteria scale-inhibiting and wax-preventing coating.
2. The method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating according to claim 1, characterized in that, The oily epoxy resin is either bisphenol A type epoxy resin or bisphenol F type epoxy resin.
3. The method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating according to claim 2, characterized in that, The bisphenol A type epoxy resin is selected from at least one of E42 epoxy resin or E44 epoxy resin; The bisphenol F type epoxy resin is F51 epoxy resin.
4. The method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating according to claim 1, characterized in that, In step (1), the ratio of the amount of oily epoxy resin, octadecylamine, curing agent and organic solvent is: 1g: 0.9g: (0.25-1)g: 2mL.
5. The method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating according to claim 1, characterized in that, In step (2), the mass ratio of polyethyleneimine to glycidyltrimethylammonium chloride in the polyethyleneimine / glycidyltrimethylammonium chloride emulsion is 1:(0.9-2).
6. The method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating according to claim 1, characterized in that, In step (3), the concentration of the aldehyde-based carbon quantum dot ethanol solution is 10-70 g / L.
7. The method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating according to claim 6, characterized in that, The preparation process of the aldehyde-based carbon quantum dots in the ethanol solution is as follows: Aldehyde compounds were mixed with anhydrous ethanol in a sealed polytetrafluoroethylene bottle, then heated, cooled, and centrifuged to obtain aldehyde-based carbon quantum dots.
8. The method for preparing an underwater self-healing superhydrophilic resistance-reducing, anti-scaling, and anti-wax coating according to claim 7, characterized in that, The volume ratio of the aldehyde compound to anhydrous ethanol is 1:2; The aldehyde compound is glutaraldehyde; The conditions for the heating process are: heating at 150°C for 4 hours.
9. The method for preparing an underwater self-healing superhydrophilic resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating according to claim 1, characterized in that, The number of times steps (2) and (3) are repeated is 3-5 times; The curing conditions are as follows: curing at 60-120℃ for 2-8 hours.
10. An underwater self-healing, super-hydrophilic, resistance-reducing, antibacterial, scale-inhibiting, and anti-wax coating, characterized in that, Prepared by the method described in any one of claims 1-9.