A super-hydrophobic antireflection self-cleaning coating material and a preparation method thereof

Abstract

The application discloses a super-hydrophobic self-cleaning coating material and a preparation method thereof. The super-hydrophobic self-cleaning coating material comprises 1-3 parts of a silicon-based mesoporous material, 4-5 parts of coconut oil diethanolamide, 1-3 parts of nano-titanium dioxide, 3-5 parts of methacrylic acid dodecanol ester, 1-3 parts of a polyethylene glycol type antistatic agent, 1-3 parts of expanded graphite, 1-3 parts of nano-graphene, 30-50 parts of anhydrous ethanol and 20-30 parts of acetone. In the application, the synergistic effect of the components is used, so that the coating has good hydrophobicity, durability, stain resistance, transmittance and antistatic property, the self-cleaning effect of the coating is good, the service time of the coating is greatly improved, and the cost of frequently replacing the coating is reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of self-cleaning materials, and particularly relates to a super-hydrophobic and anti-reflection type self-cleaning coating material and a preparation method thereof. BACKGROUND

[0002] As one of the future clean, efficient and never-depleted green energy technologies, solar energy technology has been applied more and more widely in recent years, and the solar photovoltaic glass industry, which is a combination of solar energy utilization and traditional glass industry, is becoming one of the fastest growing high-tech industries in the world and is known as a new sunrise industry. In recent years, the photovoltaic power generation industry has developed rapidly, and the installed capacity has experienced explosive growth. Due to the influence of national policies encouraging the development of distributed photovoltaic power generation, distributed photovoltaic power generation has also developed rapidly. In particular, the use of residential roof and factory roof to install distributed grid-connected photovoltaic power generation mode is encouraged and advocated.

[0003] However, in recent years, self-cleaning coatings have received widespread attention. Super-hydrophobic (water contact angle > 150°) self-cleaning coatings can remove dust by rolling water droplets, achieving a self-cleaning function similar to that of a lotus leaf. However, in the actual air environment, there are various pollutants, including hydrophilic dust pollutants, oleophilic organic pollutants, solid pollutants, liquid pollutants, and mixtures of various pollutants. The existing super-hydrophobic coatings cannot effectively remove all pollutants with different characteristics, resulting in a loss of super-hydrophobic properties on the coating surface due to the continuous accumulation of pollutants during actual use. Therefore, the existing super-hydrophobic coatings still have the problem of short service life. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a super-hydrophobic and anti-reflection type self-cleaning coating material and a preparation method thereof, aiming to provide a self-cleaning coating material with a longer service life to solve the technical problem of short service life of the existing self-cleaning coating.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0006] The present application provides the following technical solutions: a super-hydrophobic and anti-reflection type self-cleaning coating material, comprising, by weight:

[0007] 1-3 parts of a silicon-based mesoporous material;

[0008] 4-5 parts of cocoyl diethanolamide;

[0009] 1-3 parts of nano-titanium dioxide;

[0010] 3-5 parts of methacrylic acid dodecanol ester;

[0011] 1-3 parts of a polyethylene glycol type antistatic agent;

[0012] Expanded graphite 1-3 parts;

[0013] Nano-graphene 1-3 parts;

[0014] Anhydrous ethanol 30-50 parts;

[0015] Acetone 20-30 parts.

[0016] Further, the silicon-based mesoporous material is any one or more of MCM-22, MCM-41, MCM-48 and SBA-15.

[0017] Further, the nano-titanium dioxide is anatase phase crystal type with a photocatalytic function, and the particle size is 2-3 nanometers.

[0018] Further, it includes, by weight parts:

[0019] Silicon-based mesoporous material 1 part;

[0020] Nano-titanium dioxide 1 part;

[0021] Cocodiethanolamide 1-2 parts;

[0022] Methacrylic acid 1-2 parts;

[0023] Methacryloyloxytrimethylsilane 1-2 parts;

[0024] Dodecanol methacrylate 1-3 parts;

[0025] Polyethylene glycol type antistatic agent 1-3 parts;

[0026] Expanded graphite 1-3 parts;

[0027] Nano-graphene 1-3 parts;

[0028] Anhydrous ethanol 30-50 parts;

[0029] Acetone 20-30 parts.

[0030] The application also discloses a preparation method of the super-hydrophobic and anti-reflection type self-cleaning coating material, which comprises using the super-hydrophobic and self-cleaning coating for photovoltaic solar energy as described in any one of the above.

[0031] S01: ultrasonic dispersion of the silicon-based mesoporous material, nano-titanium dioxide and cocodiethanolamide in anhydrous ethanol, stirring at a certain temperature to form a first mixture;

[0032] S02: adding anhydrous ethanol, polyethylene glycol type antistatic agent and expanded graphite into the first mixture to uniformly stir to form a second mixture;

[0033] S03: adding dodecanol methacrylate, nano-graphene, and acetone to the second mixture, stirring for 30-45 min, mixing uniformly, filtering, and drying to form the self-cleaning coating material.

[0034] Further, the stirring time in the step S01 is 30-45 min, and the stirring temperature is 80-100℃.

[0035] Further, the step S03 further comprises:

[0036] stirring and mixing dodecanol methacrylate, nano-graphene, acetone, methacryloyloxytrimethylsilane, and methacrylic acid to form an intermediate product;

[0037] stirring the second mixture with the intermediate product, mixing uniformly, filtering, and drying to form the self-cleaning coating material.

[0038] Further, the step S01 further comprises:

[0039] fluorinating the surface of the silicon-based mesoporous material to introduce active reaction sites.

[0040] Further, the step S01 further comprises:

[0041] placing the silicon-based mesoporous material subjected to the fluorination surface treatment in the polyamine acetonitrile solution for 2-3 hours.

[0042] Compared with the prior art, the preparation method of the photovoltaic dustproof self-cleaning coating in the present application can oxidize and decompose various organic pollutants by using the silicon-based mesoporous material as a carrier, introducing a coconut oil diethanolamide active group, and carrying nano-titanium dioxide, and can wash various pollutants with rainwater to remove the pollutants accumulated on the surface of the photovoltaic glass plate, so that the thin film has a self-cleaning effect, and the stain resistance of the coating is improved.

[0043] By adding nano-graphene, a fluff-like structure can be formed on the surface of the coating, which can reduce the reflection of the coating, increase the thermal conductivity of the coating, accelerate the decomposition of organic matter, and have a self-cleaning function, and is conducive to absorbing light in all directions and refracting to the photovoltaic module, especially in a weak light environment, which is more conducive to absorbing scattered light, and can make the effective transmission ratio of sunlight greater than 90% or more, thereby improving the transmittance of the coating.

[0044] The surface of the expanded graphite is modified by mixing the surfactant type antistatic agent with the expanded graphite, so that the modified expanded graphite is not easy to agglomerate, can be uniformly dispersed in the silicon-based mesoporous material, and will not gradually seep out of the coating during use, so that the formed coating has permanent antistatic performance, prolongs the service life of the coating, and reduces the cost of frequent replacement of the coating.

[0045] In the application, through the synergistic effect of the above components, the coating formed has good hydrophobicity, durability, stain resistance, transmittance and antistatic property, so that the self-cleaning effect of the coating is good, the service time of the coating is greatly improved, and the cost of frequent replacement of the coating is reduced.

[0046] Other advantages, objects and features of the present application will be set forth in the following specification, and in part will be apparent from the application itself, or can be learned by practice of the application. The objectives and other advantages of the present application can be realized and obtained by the following description. BRIEF DESCRIPTION OF DRAWINGS

[0047] In order to make the purposes, technical solutions and beneficial effects of the present application clearer, the present application provides the following drawings for illustration:

[0048] Figure 1 A flowchart of a preparation method of a photovoltaic dustproof self-cleaning coating is provided for an embodiment of the present application.

[0049] Figure 2 A flowchart of step S03 is provided for an embodiment of the present application. DETAILED DESCRIPTION

[0050] Embodiment one

[0051] The present embodiment provides a super-hydrophobic and transmittance-increasing self-cleaning coating material, which comprises, according to the weight composition:

[0052] 1 part of silicon-based mesoporous material, 4 parts of cocoyl diethanolamide, 1 part of nano-titanium dioxide, 3 parts of methacrylic acid dodecanol ester, 1 part of polyethylene glycol type antistatic agent, 1 part of expanded graphite, 1 part of nano-graphene, 30 parts of anhydrous ethanol, and 20 parts of acetone.

[0053] Embodiment two

[0054] The present embodiment provides a super-hydrophobic and transmittance-increasing self-cleaning coating material, which comprises, according to the weight composition:

[0055] Silicon-based mesoporous material 2 parts; coconut oil diethanolamide 4.5 parts; nano-titanium dioxide 2 parts; methacrylic acid dodecanol ester 3 parts; polyethylene glycol type antistatic agent 1 part; expanded graphite 1 part; nano-graphene 1 part; anhydrous ethanol 30 parts; acetone 20 parts.

[0056] Example Three

[0057] The present example proposes a super-hydrophobic and anti-fouling self-cleaning coating material, which includes, by weight:

[0058] Silicon-based mesoporous material 2 parts; coconut oil diethanolamide 4.5 parts; nano-titanium dioxide 2 parts; methacrylic acid dodecanol ester 3 parts; polyethylene glycol type antistatic agent 2 parts; expanded graphite 2 parts; nano-graphene 1 part; anhydrous ethanol 30 parts; acetone 20 parts.

[0059] Example Four

[0060] The present example proposes a super-hydrophobic and anti-fouling self-cleaning coating material, which includes, by weight:

[0061] Silicon-based mesoporous material 3 parts; coconut oil diethanolamide 5 parts; nano-titanium dioxide 3 parts; methacrylic acid dodecanol ester 3 parts; polyethylene glycol type antistatic agent 2 parts; expanded graphite 2 parts; nano-graphene 1 part; anhydrous ethanol 30 parts; acetone 20 parts.

[0062] Example Five

[0063] The present example proposes a super-hydrophobic and anti-fouling self-cleaning coating material, which includes, by weight:

[0064] Silicon-based mesoporous material 3 parts; coconut oil diethanolamide 5 parts; nano-titanium dioxide 3 parts; methacrylic acid dodecanol ester 3 parts; polyethylene glycol type antistatic agent 3 parts; expanded graphite 3 parts; nano-graphene 1 part; anhydrous ethanol 30 parts; acetone 20 parts.

[0065] Example Six

[0066] The present example proposes a super-hydrophobic and anti-fouling self-cleaning coating material, which includes, by weight:

[0067] Silicon-based mesoporous material 3 parts; coconut oil diethanolamide 5 parts; nano-titanium dioxide 3 parts; methacrylic acid dodecanol ester 3 parts; polyethylene glycol type antistatic agent 3 parts; expanded graphite 3 parts; nano-graphene 2 parts; anhydrous ethanol 30 parts; acetone 20 parts.

[0068] Example Seven

[0069] The present example proposes a super-hydrophobic and anti-fouling self-cleaning coating material, which includes, by weight:

[0070] Silicon-based mesoporous material 3 parts; coconut oil diethanolamide 5 parts; nano titanium dioxide 3 parts; methacrylic acid dodecanol ester 3 parts; polyethylene glycol type antistatic agent 3 parts; expanded graphite 3 parts; nano graphene 3 parts; anhydrous ethanol 30 parts; acetone 20 parts.

[0071] Example eight

[0072] The present embodiment proposes a super-hydrophobic and anti-reflection type self-cleaning coating material, which comprises, according to the weight component:

[0073] Silicon-based mesoporous material 3 parts; coconut oil diethanolamide 5 parts; nano titanium dioxide 3 parts; methacrylic acid dodecanol ester 3 parts; polyethylene glycol type antistatic agent 3 parts; expanded graphite 3 parts; nano graphene 3 parts; anhydrous ethanol 50 parts; acetone 30 parts.

[0074] In the present application, by taking silicon-based mesoporous material as a carrier, introducing coconut oil diethanolamide active groups, and carrying nano titanium dioxide, various organic pollutants can be oxidized and decomposed, and rainwater can be used to wash various pollutants, thereby removing the pollutants accumulated on the surface of photovoltaic glass panels, so that the film has a self-cleaning effect; the pollution resistance of the coating is improved; by adding nano graphene, a fluff-like structure can be formed on the surface of the coating, which can reduce the reflection of the coating, increase the thermal conductivity of the coating, accelerate the decomposition of organic matter and the self-cleaning function, and is conducive to absorbing light in all directions and refracting to photovoltaic components, especially in weak light environment, which is more conducive to absorbing scattered light, so that the effective transmission ratio of sunlight can be greater than 90%, and the anti-reflection property of the coating is improved; by mixing the surfactant type antistatic agent with the expanded graphite, the surface of the expanded graphite is modified, the modified expanded graphite is not easy to agglomerate, the expanded graphite can be uniformly dispersed in the silicon-based mesoporous material, and the coating will not gradually seep out during use, so that the formed coating has permanent antistatic property, prolonging the service life of the coating and reducing the cost of frequent replacement of the coating. Through the synergistic effect of the above components, the coating formed has good hydrophobicity, durability, pollution resistance, anti-reflection property and antistatic property, so that the self-cleaning effect of the coating is good, the service time of the coating is greatly improved, and the cost of frequent replacement of the coating is reduced.

[0075] Table 1 Performance test results of examples 1-8

[0076]

[0077]

[0078] As can be seen from the performance detection table of examples 1-8 in the above table 1, with the increase of the content of nano-titanium dioxide, the antifouling effect is obviously enhanced, which is due to the photo-induced hydrophilic property of nano-titanium dioxide, and titanium dioxide can directly utilize various ways of ultraviolet light including sunlight to oxidize and decompose various organic pollutants; with the increase of the content of expanded graphite and polyethylene glycol antistatic agent, the service life of the coating is significantly enhanced; with the increase of the content of nano-graphene, the transmittance of the coating is significantly enhanced.

[0079] Preferably, the silicon-based mesoporous material is any one or more of MCM-22, MCM-41, MCM-48 and SBA-15. For example, the silicon-based mesoporous material is a mixture of MCM-22 and MCM-41, a mixture of MCM-41 and MCM-48, a mixture of MCM-48 and SBA-15, a mixture of MCM-22 and SBA-15, a mixture of MCM-41 and MCM-48, a mixture of SBA-15, etc.

[0080] Preferably, the nano-titanium dioxide is an anatase phase crystal type with photocatalytic function, and the particle size of the nano-titanium dioxide is 2-3 nanometers. For example, the particle size can be 2 nanometers, 2.2 nanometers, 2.4 nanometers, 2.6 nanometers, 2.8 nanometers, 3 nanometers, etc. Of course, in this application, the particle size of the nano-titanium dioxide can also be other values according to actual conditions and specific needs, which is not limited here.

[0081] Preferably, in this application, an ultrahydrophobic and transmittance-enhancing self-cleaning coating material is also provided, which comprises, by weight:

[0082] 1 part of silicon-based mesoporous material, 1 part of nano-titanium dioxide, 1-2 parts of coconut diethanolamide, 1-2 parts of methacrylic acid, 1-2 parts of methacryloxytrimethylsilane, 1-3 parts of dodecanol methacrylate, 1-3 parts of polyethylene glycol antistatic agent, 1-3 parts of expanded graphite, 1-3 parts of nano-graphene, 30-50 parts of anhydrous ethanol, 20-30 parts of acetone.

[0083] In this application, the coconut diethanolamide is 1-2 parts by weight percentage, for example, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.8 parts, 2 parts, etc.

[0084] In this application, the methacryloxytrimethylsilane is 1-2 parts by weight percentage, for example, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.8 parts, 2 parts, etc.

[0085] In this application, the dodecanol methacrylate is 1-3 parts by weight percentage, for example, 1 part, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, etc.

[0086] In the present application, in addition to the direct use of various ways of ultraviolet light including sunlight to nano titanium dioxide, the oxidation and decomposition of various organic pollutants, and the introduction of methacrylic acid, methacryloxytrimethylsilane, and dodecanol methacrylate, which will react with the active groups of coconut diethanolamide, further enhance the stain resistance of the coating, thereby significantly improving the stain resistance of the coating.

[0087] In the present application, please refer to Figure 1 As shown, a preparation method of a super-hydrophobic and anti-reflection type self-cleaning coating material is also disclosed, which comprises using the super-hydrophobic and self-cleaning coating for photovoltaic solar energy as described in any one of the above, and the preparation method comprises the following steps:

[0088] S01: ultrasonic dispersion of the silicon-based mesoporous material, nano titanium dioxide, and coconut diethanolamide in absolute ethanol, stirring at a certain temperature to form a first mixture;

[0089] S02: adding absolute ethanol, polyethylene glycol type antistatic agent, and expanded graphite to the first mixture and stirring uniformly to form a second mixture;

[0090] S03: adding dodecanol methacrylate, nano graphene, and acetone to the second mixture, stirring for 30-45 min, mixing uniformly, filtering, and drying to form a self-cleaning coating material.

[0091] In the present application, by introducing the active groups of coconut diethanolamide and reacting with nano titanium dioxide to form a reactive site deposited on the carrier of the silicon-based mesoporous material, the oxidation and decomposition of various organic pollutants are greatly improved, and the pollutants accumulated on the surface of the photovoltaic glass plate are washed away by rainwater, so that the film has a self-cleaning effect; the stain resistance of the coating is improved;

[0092] By stirring uniformly with absolute ethanol, polyethylene glycol type antistatic agent, and expanded graphite, the surface of the expanded graphite can be modified, so that the expanded graphite is not easy to agglomerate and can be uniformly dispersed in the silicon-based mesoporous material, greatly improving the service time of the coating and making the coating more durable;

[0093] Finally, by adding nano graphene, the nano graphene covers the mixture with the silicon-based mesoporous material as the carrier, greatly improving the anti-reflection property of the coating and greatly improving the performance of the coating.

[0094] Further, the stirring time in the step S01 is 30-45 minutes, and the stirring temperature is 80-100℃. Preferably, the stirring time in the step S01 can be specifically 30 minutes, 33 minutes, 36 minutes, 38 minutes, 40 minutes, 42 minutes, 45 minutes, etc.; the stirring temperature can be specifically 80℃, 85℃, 90℃, 95℃, 100℃, etc., which is adjusted in real time according to the actual situation and specific needs, and is not limited here.

[0095] Further, please refer to Figure 1 As shown in the step S03, the step S03 further comprises:

[0096] Stirring, mixing methacrylic acid dodecanol ester, nano graphene, acetone, methyl methacryloyloxy trimethylsilane, methyl methacrylate to form an intermediate product;

[0097] Stirring, mixing the second mixture with the above-mentioned intermediate product, filtering, drying to form a self-cleaning coating material.

[0098] In the present application, by adding methyl methacryloyloxy trimethylsilane, methyl methacrylate, dodecanol methyl methacrylate and other stain-resistant materials, which will react with coconut oil diethanolamide active points and nano titanium dioxide, further greatly improving the stain resistance and service performance of the coating.

[0099] Further, the step S01 further comprises: fluorinated surface treatment of the silicon-based mesoporous material to introduce active reaction sites.

[0100] In the present application, by fluorinated surface treatment of the silicon-based mesoporous material, on the one hand, the silicon-based mesoporous material forms a soft porous foam layer, which can disperse the interface layer stress and absorb impact energy, thereby improving the toughness of the coating; on the other hand, it can be covalently connected with nano titanium dioxide in multiple directions, greatly enhancing the bonding strength of the silicon-based mesoporous material and nano titanium dioxide, thereby improving the service life of the self-cleaning coating.

[0101] Further, the step S01 further comprises:

[0102] The silicon-based mesoporous material subjected to fluorinated surface treatment is placed in a polyamine acetonitrile solution for 2-3 hours. By placing in a polyamine acetonitrile reaction, a soft porous foam layer is formed. Specifically, in the present embodiment, the reaction time can be 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, etc.

[0103] Finally, it should be noted that the above preferred embodiments are merely intended to illustrate the technical solutions of the present application but not to limit the present application. Although the present application has been described in detail through the above preferred embodiments, those skilled in the art should understand that various modifications can be made in form and details without departing from the scope of the present application defined by the claims.

Claims

1. A superhydrophobic, antireflective, self-cleaning coating material, characterized by, According to the weight ingredients include: Silicon-based mesoporous material 1-3 parts; Cocoyl diethanolamide 4-5 parts; Nano titanium dioxide 1-3 parts; Methacrylic acid dodecanol ester 3-5 parts; Polyethylene glycol type antistatic agent 1-3 parts; Expanded graphite 1-3 parts; Nano graphene 1-3 parts; Anhydrous ethanol 30-50 parts; Acetone 20-30 parts. 2.The super-hydrophobic, anti-reflection, self-cleaning coating material according to claim 1, characterized in that, The silicon-based mesoporous material is any one or more of MCM-22, MCM-41, MCM-48 and SBA-15. 3.The super-hydrophobic, anti-reflection, self-cleaning coating material according to claim 1, characterized in that, The nano titanium dioxide is anatase phase crystal form with photocatalytic function, and the particle size is 2-3 nanometers.

4. A superhydrophobic, antireflective, self-cleaning coating material, characterized by, According to the weight ingredients include: Silicon-based mesoporous material 1 part; Nano titanium dioxide 1 part; Cocoyl diethanolamide 1-2 parts; Methacrylic acid 1-2 parts; Methacryloyloxytrimethylsilane 1-2 parts; Methacrylic acid dodecanol ester 1-3 parts; Polyethylene glycol type antistatic agent 1-3 parts; Expanded graphite 1-3 parts; Nano graphene 1-3 parts; Anhydrous ethanol 30-50 parts; Acetone 20-30 parts.

5. A method for preparing a superhydrophobic, antireflective, self-cleaning coating material, characterized by, It includes using the super-hydrophobic and anti-reflection type self-cleaning coating material as claimed in any one of claims 1 to 4, and the preparation method thereof includes the following steps: S01: ultrasonic dispersion of silicon-based mesoporous material, nano titanium dioxide, cocoyl diethanolamide in anhydrous ethanol, stirring at a certain temperature to form a first mixture; S02: adding anhydrous ethanol, polyethylene glycol type antistatic agent, expanded graphite to the first mixture and stirring uniformly to form a second mixture; S03: adding methacrylic acid dodecanol ester, nano graphene, acetone to the second mixture, stirring for 30-45 min, mixing uniformly, filtering and drying to form a self-cleaning coating material.

6. The method according to claim 5, wherein the method is characterized by: The stirring time in step S01 is 30-45 minutes, and the stirring temperature is 80-100℃.

7. The method according to claim 5, wherein the method is characterized by: The step S03 further includes: Stirring and mixing methacrylic acid dodecanol ester, nano graphene, acetone, methacryloyloxytrimethylsilane and methacrylic acid to form an intermediate product; Stirring and mixing the second mixture with the above intermediate product, filtering and drying to form a self-cleaning coating material. 8.The method according to claim 5, wherein: The step S01 further includes: Fluorinated surface treatment of the silicon-based mesoporous material to introduce active reaction sites.

9. The method according to claim 8, wherein the method is characterized by: The step S01 further includes: Placing the silicon-based mesoporous material subjected to fluorinated surface treatment in a polyamine acetonitrile solution for 2-3 hours.

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