Transparent antifouling paint applied to surface of marine photoelectric equipment and preparation method of transparent antifouling paint

Abstract

The invention provides a transparent antifouling paint applied to the surface of marine optoelectronic equipment and a preparation method thereof. The coating is prepared from the following components in percentage by mass: 10%-40% of polyether polyol, 5%-20% of isocyanate, 5%-45% of monohydroxypropyl silicone oil, 2%-10% of acetylated cyclodextrin, 1%-5% of an antifouling agent, 20%-50% of a solvent and 0.05%-0.5% of a catalyst, the anti-fouling agent is complexed in a cavity of acetylated cyclodextrin through the host-guest interaction, so that the slow release of the anti-fouling agent is realized; the acetylated cyclodextrin is connected to a polymer main chain through a covalent bond; the monohydroxypropyl silicone oil is anchored in a polymer matrix through a covalent bond, so that long-acting lubrication of the surface of the coating is realized; meanwhile, the coating has excellent adhesion to substrates such as glass, organic glass and epoxy resin, adhesion of inorganic and organic pollutants on the surface of the coating can be remarkably reduced, long-acting transparency under seawater is achieved, and the coating can be widely applied to antifouling of the surface of marine photoelectric equipment.

Description

Technical Field

[0001] The invention belongs to the technical field of antifouling coating preparation, and in particular relates to a transparent antifouling coating applied to the surface of marine optoelectronic equipment and a preparation method thereof. Background Art

[0002] With the continuous development of high-tech, the demand for energy in modern society is increasing. In recent years, clean energy such as marine photovoltaics has penetrated rapidly. However, due to the extremely complex marine environment and the rich biological species, the surface of photovoltaic cells immersed in seawater is inevitably attached with biological fouling. This greatly affects the efficiency of photoelectric conversion. Therefore, an effective way to solve the problem of marine biofouling is urgently needed.

[0003] The use of antifouling coatings to inhibit the attachment of biofouling has been proven to be effective. Antifouling coatings can be divided into fouling resistance coatings and fouling release coatings according to their different working principles.

[0004] Specifically, the fouling resistance coating is a coating that contains antifouling agents. The advantage of this coating is that it has a good static antifouling effect. The disadvantage is that the antifouling process is not highly controllable and has a limited service life. The fouling release coating itself does not contain antifouling agents, and prevents marine fouling organisms from attaching and adhering to the coating surface through its own physical properties. The advantage of this coating is that it has a long service life and is environmentally friendly. The disadvantage is that this coating relies on water flow shear desorption of fouling, and the static antifouling effect is not good.

[0005] For the surface antifouling of marine photovoltaic equipment, on the one hand, it is required to have excellent antifouling performance so that its surface does not adhere to biological fouling. On the other hand, the antifouling coating is required to have high transparency and will not reduce the efficiency of photoelectric conversion.

[0006] The antifouling coatings currently on the market still have the following problems when applied to the field of underwater transparent antifouling: 1. The coating has poor transparency underwater; 2. The problem of explosive release of antifouling agents caused by physical blending of antifouling agents; 3. The coating has poor adhesion to the substrate underwater. Summary of the invention

[0007] In view of the deficiencies of the prior art, the purpose of the present invention is to provide a transparent antifouling coating applied to the surface of marine optoelectronic equipment, wherein the polymer substrate is silicone-modified polyurethane, the drug carrier cyclodextrin is covalently bonded into the polymer main chain, and the host-guest interaction between cyclodextrin and drug molecules is used to achieve the slow release of the drug, which can not only achieve the slow release of the drug, but also can be firmly attached to the substrate. At the same time, the coating can maintain a long-term transparent effect and good antifouling durability in the seawater environment, and has a wide range of application prospects in the field of antifouling of optoelectronic equipment surfaces in the marine environment.

[0008] Another object of the present invention is to provide a method for preparing an antifouling coating applied to the surface of marine optoelectronic equipment, which is scientific, reasonable, simple and easy to implement.

[0009] The technical solution adopted by the present invention is as follows:

[0010] The transparent antifouling coating applied to the surface of marine optoelectronic equipment is prepared from the following raw materials in percentage by mass:

[0011] Polyether polyol: 10%-40%;

[0012] Isocyanate: 5%-20%;

[0013] Silicone oil: 5%-45%;

[0014] Acetylated cyclodextrin: 2%-10%;

[0015] Antifouling agent: 1%-5%;

[0016] Solvent: 20%-50%;

[0017] Catalyst: 0.05%-0.5%.

[0018] The preparation method of the acetylated cyclodextrin is:

[0019] (1) dissolving β-cyclodextrin in a certain volume of N,N-dimethylformamide and stirring to obtain a transparent solution;

[0020] (2) adding a certain volume of acetic anhydride to the above solution and reacting at 20-80° C. for 12-48 hours;

[0021] (3) adding the above solution after the reaction into a large amount of acetone or acetonitrile for washing, and centrifuging the precipitate;

[0022] (4) The solid after centrifugation is freeze-dried to obtain acetylated cyclodextrin.

[0023] The mass ratio of the beta-cyclodextrin to acetic anhydride is 0.5-1.

[0024] The mass ratio of the beta-cyclodextrin to N,N-dimethylformamide is 0.1-0.3.

[0025] The transparent antifouling coating applied to the surface of marine optoelectronic equipment has the structural formula:

[0026]

[0027] The polyether polyol is polytetramethylene ether diol with a molecular weight of 1000-3000.

[0028] The isocyanate is one or more of isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate and 1,4-cyclohexane diisocyanate, and has a molecular weight of 1000-3000.

[0029] The silicone oil is a single-end hydroxypropyl terminated silicone oil with a molecular weight of 1000-5000.

[0030] The antifouling agent is one or more of eugenol, cinnamaldehyde and coumarin.

[0031] The solvent is one or more of tetrahydrofuran, 1,4-dioxane and N,N-dimethylformamide.

[0032] The catalyst is an organic tin catalyst.

[0033] The construction process of the transparent antifouling paint is spraying, rolling or brushing.

[0034] Furthermore, the present invention also provides a method for preparing a transparent antifouling coating applied to the surface of a marine optoelectronic device, the steps of which are as follows:

[0035] (1) First, polytetrahydrofuran ether diol is dissolved in a mixed solvent of DMF / THF, and isocyanate is added after stirring evenly, and the mixture is placed at 60-90° C. for reaction for 2-6 hours;

[0036] (2) adding acetylated cyclodextrin to the product after the above reaction, stirring until uniformly dissolved, adding an organic tin catalyst, and reacting at 60-90° C. for 2-6 hours;

[0037] (3) Adding the silicone oil terminated with a single hydroxypropyl group to the solution after the reaction in (2) and reacting at 60-90° C. for 2-6 hours.

[0038] (4) The product after the reaction is sprayed, rolled, or brushed on the surface of glass, polymethyl methacrylate, or epoxy resin, and the solvent is evaporated at 25-80° C. for 24-120 hours to obtain a transparent antifouling coating that can be applied to the surface of marine photovoltaic equipment.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] The present invention introduces a single-end functionalized organosilicon chain segment into a polymer molecular chain through a covalent bond, effectively solving the problem of easy loss of lubricant in traditional lubricant-mediated coatings. Due to the low surface energy characteristics of the organosilicon chain segment, it will spontaneously migrate to the surface of the coating to form a liquid-like layer, greatly increasing the stability of the lubricated surface.

[0041] The prepared coating has a low water swelling rate in seawater environment, does not cause water molecules to aggregate in the polymer molecular chain, and can maintain long-term transparency. Thanks to the low swelling rate of water molecules, it is difficult for water molecules to destroy the non-covalent bond between the polymer coating and the substrate, so the coating exhibits excellent adhesion in seawater environment.

[0042] The host-guest complex constructed based on the host-guest recognition strategy can effectively achieve the sustained release of the antifouling agent, increase the service life of the antifouling agent, and extend the service life of the antifouling coating. DETAILED DESCRIPTION

[0043] In order to better understand the above technical scheme, exemplary embodiments of the present invention will be described in more detail below. Although exemplary embodiments of the present invention are shown below, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a clearer and more thorough understanding of the present invention, and to be able to fully convey the scope of the present invention to those skilled in the art.

[0044] Example 1

[0045] The transparent antifouling coating applied to the surface of marine optoelectronic equipment is prepared from the following raw materials in percentage by mass:

[0046] Polytetramethylene glycol: 22%;

[0047] Isophorone diisocyanate: 10%;

[0048] Monohydroxypropyl silicone oil: 5%;

[0049] Acetylated cyclodextrin: 2.5%;

[0050] Eugenol: 0.45%;

[0051] Solvent: 60%;

[0052] Dibutyltin dilaurate: 0.05%;

[0053] The method for preparing the transparent antifouling coating applied to the surface of marine optoelectronic equipment comprises the following steps:

[0054] (1) First, polytetrahydrofuran ether diol is dissolved in a mixed solvent of DMF / THF, and isophorone diisocyanate is added after stirring evenly, and the mixture is placed at 80° C. for 4 hours;

[0055] (2) adding acetylated cyclodextrin to the product after the above reaction, stirring until uniformly dissolved, adding dibutyltin dilaurate, and reacting at 80° C. for 2 h;

[0056] (3) Add the single-end hydroxypropyl-terminated silicone oil to the above mixture and continue the reaction at 80° C. for 2 h.

[0057] (4) The product after the reaction was sprayed on the glass surface, and the solvent was evaporated at 25° C. for 120 hours.

[0058] Example 2

[0059] The transparent antifouling coating applied to the surface of marine optoelectronic equipment is prepared from the following raw materials in percentage by mass:

[0060] Polytetramethylene glycol: 21%;

[0061] Isophorone diisocyanate: 9%;

[0062] Monohydroxypropyl silicone oil: 5%;

[0063] Acetylated cyclodextrin: 4.2%;

[0064] Eugenol: 0.75%;

[0065] Solvent: 60%;

[0066] Dibutyltin dilaurate: 0.05%;

[0067] The preparation method of the transparent antifouling coating applied to the surface of marine optoelectronic equipment has the same steps as Example 1.

[0068] Example 3

[0069] The transparent antifouling coating applied to the surface of marine optoelectronic equipment is prepared from the following raw materials in percentage by mass:

[0070] Polytetramethylene glycol: 20%;

[0071] Isophorone diisocyanate: 8%;

[0072] Monohydroxypropyl silicone oil: 5%;

[0073] Acetylated cyclodextrin: 6%;

[0074] Eugenol: 0.95%;

[0075] Solvent: 60%;

[0076] Dibutyltin dilaurate: 0.05%;

[0077] The preparation method of the transparent antifouling coating applied to the surface of marine optoelectronic equipment has the same steps as Example 1.

[0078] Example 4

[0079] Polytetramethylene glycol: 17%;

[0080] Isophorone diisocyanate: 10%;

[0081] Monohydroxypropyl silicone oil: 10%;

[0082] Acetylated cyclodextrin: 2.5%;

[0083] Eugenol: 0.45%;

[0084] THF / DMF: 60%;

[0085] Dibutyltin dilaurate: 0.05%;

[0086] The preparation method of the transparent antifouling coating applied to the surface of marine optoelectronic equipment has the same steps as Example 1.

[0087] Example 5

[0088] The transparent antifouling coating applied to the surface of marine optoelectronic equipment is prepared from the following raw materials in percentage by mass:

[0089] Polytetramethylene glycol: 12%;

[0090] Isophorone diisocyanate: 10%;

[0091] Monohydroxypropyl silicone oil: 15%;

[0092] Acetylated cyclodextrin: 2.5%;

[0093] Eugenol: 0.45%;

[0094] THF / DMF: 60%;

[0095] Dibutyltin dilaurate: 0.05%;

[0096] The preparation method of the transparent antifouling coating applied to the surface of marine optoelectronic equipment has the same steps as Example 1.

[0097] Example 6

[0098] The transparent antifouling coating applied to the surface of marine optoelectronic equipment is prepared from the following raw materials in percentage by mass:

[0099] Polytetramethylene glycol: 2%;

[0100] Isophorone diisocyanate: 10%;

[0101] Monohydroxypropyl silicone oil: 25%;

[0102] Acetylated cyclodextrin: 2.5%;

[0103] Eugenol: 0.45%;

[0104] THF / DMF: 60%;

[0105] Dibutyltin dilaurate: 0.05%;

[0106] The preparation method of the transparent antifouling coating applied to the surface of marine optoelectronic equipment has the same steps as Example 1.

[0107] Comparative Example 1

[0108] The transparent antifouling coating applied to the surface of marine optoelectronic equipment is prepared from the following raw materials in percentage by mass:

[0109] Polytetramethylene glycol: 25%;

[0110] Isophorone diisocyanate: 10%;

[0111] Acetylated cyclodextrin: 4.5%;

[0112] Eugenol: 0.5%;

[0113] THF / DMF: 60%;

[0114] Dibutyltin dilaurate: 0.05%;

[0115] The method for preparing the transparent antifouling coating applied to the surface of marine optoelectronic equipment comprises the following steps:

[0116] (1) First, polytetrahydrofuran ether diol is dissolved in a mixed solvent of DMF / THF, and isophorone diisocyanate is added after stirring evenly, and the mixture is placed at 80° C. for 4 hours;

[0117] (2) adding acetylated cyclodextrin to the product after the above reaction, stirring until uniformly dissolved, adding dibutyltin dilaurate, and reacting at 80° C. for 2 h;

[0118] (3) The product after the reaction was sprayed on the glass surface, and the solvent was evaporated at 25° C. for 120 hours.

[0119] Comparative Example 2

[0120] The transparent antifouling coating applied to the surface of marine optoelectronic equipment is prepared from the following raw materials in percentage by mass:

[0121] Polytetramethylene glycol: 15%;

[0122] Isophorone diisocyanate: 9.95%;

[0123] Monohydroxypropyl silicone oil 15%;

[0124] THF / DMF: 60%;

[0125] Dibutyltin dilaurate: 0.05%;

[0126] The method for preparing the transparent antifouling coating applied to the surface of marine optoelectronic equipment comprises the following steps:

[0127] (1) First, polytetrahydrofuran ether diol is dissolved in a mixed solvent of DMF / THF, and isophorone diisocyanate is added after stirring evenly, and the mixture is placed at 80° C. for 4 hours;

[0128] (3) Add the single-end hydroxypropyl-terminated silicone oil to the above mixture and continue the reaction at 80° C. for 2 h.

[0129] (4) The product after the reaction was sprayed on the glass surface, and the solvent was evaporated at 25° C. for 120 hours.

[0130] Comparative Example 3

[0131] The material used for comparison is commercial Dow Corning 184, which is composed of the following raw materials in percentage by mass:

[0132] Main agent: 35%;

[0133] Catalyst: 3.5%;

[0134] Xylene: 61.5%

[0135] The construction process is brush coating, mix the above mixture evenly and then brush it on the surface of the protective equipment;

[0136] The experimental results are shown in the following table:

[0137]

[0138]

[0139] From the experimental results of the embodiments and comparative examples, the embodiments can effectively inhibit bacteria and algae from settling on their surfaces, and the antibacterial and anti-algae rates of all embodiments are greater than 91%. Among all the embodiments, the antibacterial and anti-algae conditions of Example 6 are the best, which is attributed to the low surface energy, low elastic modulus, super-lubricating surface and effective sterilization of antifouling agents. Examples 1-3 explore the effect of different amounts of bactericide addition on the antifouling effect of the coating, wherein as the amount of cyclodextrin / eugenol complex added increases, the antibacterial and anti-algae effects of the coating are enhanced. Examples 4-6 fix the amount of cyclodextrin / eugenol added, explore the effect of different amounts of silicone oil added on the antifouling performance of the coating, and as the amount of silicone oil added increases, the antifouling effect of the coating is enhanced, which is attributed to the silicone oil reducing the surface energy and enhancing the super-lubricating properties of the coating. Comparative Example 1 does not add silicone oil, and the antifouling effect obtained is average. Comparative Example 2 does not add antifouling agent, and the antifouling effect is average. This shows that the coating can achieve a better antifouling effect by relying on active antifouling agent release and passive super-slip surface synergistic antifouling. The antibacterial and antialgae effects of all the examples are better than those of comparative example 3.

[0140] It can be seen from the above description that the present invention has the following advantages: excellent antibacterial and anti-algae properties. The antifouling performance of the coating is enhanced by active bactericide release and passive super-slippery surface synergistic antifouling. The prepared coating has excellent visible light transmittance and can remain transparent for a long time underwater. The antifouling agent release system is constructed through the host-guest interaction of cyclodextrin / eugenol, which prolongs the antifouling period of the antifouling coating.

[0141] The technical scope of the present invention is not limited to the contents in the above description. Those skilled in the art can make various deformations and modifications to the above embodiments without departing from the technical idea of ​​the present invention, and these deformations and modifications should all fall within the protection scope of the present invention.

Claims

1. A transparent antifouling coating applied to the surface of marine optoelectronic equipment, characterized in that: The invention is prepared from the following raw materials in percentage by mass: polyether polyol: 10%-40%, isocyanate: 5%-20%, silicone oil: 5%-45%, acetylated cyclodextrin: 2%-10%, antifouling agent: 1%-5%, solvent: 20%-50%, and catalyst: 0.05%-0.5%.

2. The transparent antifouling coating for use on the surface of marine optoelectronic equipment according to claim 1, characterized in that: The structural formula of the transparent antifouling coating is:

3. The transparent antifouling coating applied to the surface of marine optoelectronic equipment according to claim 1 or 2, characterized in that: The preparation method of the acetylated cyclodextrin is: (1) dissolving β-cyclodextrin in a certain volume of N,N-dimethylformamide and stirring to obtain a transparent solution; (2) adding a certain volume of acetic anhydride to the above solution and reacting at 20-80° C. for 12-48 hours; (3) adding the above solution after the reaction into a large amount of acetone or acetonitrile for washing, and centrifuging the precipitate; (4) The solid after centrifugation is freeze-dried to obtain acetylated cyclodextrin.

4. The transparent antifouling coating for use on the surface of marine optoelectronic equipment according to claim 3, characterized in that: The polyether polyol is polytetramethylene ether diol with a molecular weight of 1000-3000; the isocyanate is one or more of isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate and 1,4-cyclohexane diisocyanate with a molecular weight of 1000-3000.

5. The transparent antifouling coating for use on the surface of marine optoelectronic equipment according to claim 3, characterized in that: The silicone oil is a single-end hydroxypropyl terminated silicone oil with a molecular weight of 1000-5000.

6. The transparent antifouling coating for use on the surface of marine optoelectronic equipment according to claim 3, characterized in that: The antifouling agent is one or more of eugenol, cinnamaldehyde and coumarin.

7. The transparent antifouling coating for use on the surface of marine optoelectronic equipment according to claim 3, characterized in that: The solvent is one or more of tetrahydrofuran, 1,4-dioxane and N,N-dimethylformamide.

8. The transparent antifouling coating for use on the surface of marine optoelectronic equipment according to claim 3, characterized in that: The catalyst is an organic tin catalyst.

9. The transparent antifouling coating for use on the surface of marine optoelectronic equipment according to claim 3, characterized in that: The coating is applied by spraying, rolling or brushing.

10. The method for preparing a transparent antifouling coating applied to the surface of marine optoelectronic equipment according to claim 3, characterized in that: Here are the steps: Step 1, first dissolve polytetrahydrofuran ether diol in a mixed solvent of DMF / THF, stir evenly, add isocyanate, and place the mixture at 60-90° C. to react for 2-6 hours; Step 2, adding acetylated cyclodextrin to the product after the above reaction, stirring until uniformly dissolved, adding an organic tin catalyst, and reacting at 60-90° C. for 2-6 hours; Step 3, adding the silicone oil capped with a single hydroxypropyl group to the solution after the reaction in (2), and reacting at 60-90° C. for 2-6 hours; Step 4: spray, roll or brush the product after the reaction onto the surface of glass, methyl methacrylate or epoxy resin, evaporate the solvent at 25-80° C. for 24-120 hours, and obtain a transparent antifouling coating that can be applied to the surface of marine optoelectronic equipment.

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