A method for preparing bionic mucus antifouling polymer

Abstract

The invention belongs to the technical field of preparation of marine antifouling materials, and specifically relates to a method for preparing a bionic mucus antifouling polymer. Firstly, a zwitterion with strong anti-protein property contained in fish mucus is synthesized, and then grafted onto a silicone ester polymer chain segment through a double bond polymerization reaction, so as to prepare a marine bionic mucus antifouling polymer with strong anti-protein adsorption, wherein the anti-protein property of the novel zwitterion is far superior to that of a traditional zwitterion, and the grafting density is controllable; after the antifouling polymer is incorporated into the silicone coating, a dense dynamic gel layer can be formed at the interface between the silicone main coating surface and the seawater in a seawater environment, thereby achieving the purpose of antifouling; the principle of grafting the zwitterion contained in the synthesized fish epidermal mucus and the silicone ester polymer onto its chain segment through double bonds is scientific and reliable, the operation is easy to implement, and the method has great application potential in the field of marine antifouling.

Description

Technical field:

[0001] The present invention belongs to the technical field of preparation of marine antifouling materials, and specifically relates to a method for preparing a bionic mucus antifouling polymer. The prepared bionic mucus antifouling polymer is used in combination with an organosilicon coating to protect the surface of a hull from fouling. Background technology:

[0002] Marine biofouling refers to the phenomenon that fouling organisms (such as microorganisms, plants, algae or animals) attach to the surface of underwater substrates and cause harm, which seriously affects the normal operation of ships and underwater equipment. It is a problem that must be faced in marine production activities. According to statistics, severe biofouling can increase ship power and fuel consumption by 86% and 40% respectively, causing losses of up to billions of dollars each year, while also increasing energy consumption and carbon dioxide emissions. Therefore, the research and development of new marine antifouling materials is of great significance to the protection of the marine environment and the sustainable development of related industries.

[0003] The environmental problems caused by the traditional copper-containing biocide antifouling materials that were previously used in large quantities have become increasingly prominent. Countries such as Europe and the United States have been committed to developing environmentally friendly antifouling materials as alternatives. Among them, bionic antifouling is an important means and development direction for the development of environmentally friendly antifouling materials. At present, the research and development of bionic antifouling materials mainly focus on two ideas: one is to extract and imitate the active substances contained in organisms, that is, biological antifouling agents; the other is to imitate the antifouling properties and principles of the epidermis (or shell) of organisms. For the first idea, more than 30 kinds of antifouling active compounds obtained from marine organisms, including organic acids, terpenes, phenols, indoles, etc., have been reported abroad. However, natural active substances have problems such as difficulty in extraction, limited output, and long certification and approval cycle, which makes engineering applications more difficult. Therefore, it is more practical to develop bionic antifouling materials based on the antifouling properties of the material itself.

[0004] Most organisms that live in the ocean for a long time are covered with a layer of mucus, which forms a dynamic gel layer under the action of water flow, making it difficult for marine fouling organisms to identify and attach. Based on this principle, a zwitterion contained in fish epidermal mucus is first synthesized, and then grafted onto an organic silicone ester polymer through a double bond polymerization reaction to prepare a marine bionic mucus polymer material to solve the problem of marine biofouling. Among them, the silicone ester polymer is an organosilicon ester marine antifouling material disclosed in Chinese patent 201911127466.7, including dihydroxy silicone and dicarboxyl compounds, which are heated under acidic conditions in a certain ratio to undergo esterification reaction to synthesize silicone ester marine antifouling materials; wherein the dihydroxy silicone includes: hydroxy silicone oil (molecular weight of 500-10000), hydroxypropyl silicone oil (molecular weight of 500-5000); the dicarboxyl compounds include: itaconic acid, succinic acid, fumaric acid, citric acid, isophthalic acid and oxalic acid; the molar ratio of dihydroxy silicone to dicarboxyl substances is 1:1; it utilizes the hydrolysis effect of ester bonds to hydrolyze silicone oil in a seawater environment, thereby forming a silicone oil layer on the surface of the silicone matrix material to prevent the attachment of fouling organisms and achieve the purpose of antifouling. Summary of the invention:

[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and to develop a method for preparing a bionic mucus antifouling polymer to prepare a bionic mucus antifouling polymer that can be used in conjunction with an organosilicon antifouling coating to enhance the static antifouling ability and drag reduction effect of the organosilicon antifouling coating.

[0006] In order to achieve the above-mentioned purpose, the process of the preparation method of the biomimetic mucus antifouling polymer of the present invention is as follows: first, a zwitterion contained in the epidermal mucus of fish: trimethylamine nitroxide (TMAO) is synthesized, and then the trimethylamine nitroxide is grafted onto the organic silicone ester polymer by double bond polymerization to obtain the biomimetic mucus antifouling polymer; the specific process is as follows:

[0007] (1) Preparation of TMAO

[0008] Dissolving the precursor in water and mixing evenly to obtain a dimethylaminoethyl methacrylate aqueous solution with a mass percentage concentration of 30-40%;

[0009] A 30% by mass percent hydrogen peroxide aqueous solution was dripped into a dimethylaminoethyl methacrylate aqueous solution, and an oil bath reaction was performed at a temperature of 60° C. for 6 hours, wherein the mass ratio of the hydrogen peroxide aqueous solution to the dimethylaminoethyl methacrylate aqueous solution was 3:2;

[0010] The reaction solution was cooled to room temperature, frozen for 12 h, and dried for 12 h to obtain TMAO;

[0011] Precursors include 2-(dimethylamino)ethyl methacrylate, N-[(3-(dimethylamino)propyl]methacrylamide, (2-dimethylaminoethyl)methacrylate;

[0012] TMAO is a zwitterion with double bonds and strong anti-protein properties extracted from fish epidermal mucus. Its positive and negative ions are close to each other, and it has strong electrostatic induction and hydration capabilities. It can form a dense hydration layer on the surface of the substrate, has excellent ability to inhibit the attachment of fouling organisms, is not easily affected by the pH value of the environment, and has good thermal stability.

[0013] (2) Preparation of biomimetic mucus antifouling polymer

[0014] dissolving an organosilicone ester polymer in dichloromethane to obtain an emulsion;

[0015] Dissolve TMAO in methanol and then drop it into the emulsion to obtain a mixed solution;

[0016] Add 1% ammonium persulfate aqueous solution to the mixed solution, and react in an oil bath at 60°C for 10-12h.

[0017] After the reaction solution is cooled to room temperature, methanol is added dropwise to precipitate the product, which is then washed with water or methanol and centrifuged 3-4 times, and then dried at 60° C. for 48 hours to obtain a bionic mucus antifouling polymer.

[0018] The mass ratio of the organosilicon ester polymer to dichloromethane is 0.6-1, the mass ratio of TMAO to methanol to the emulsion is 1:4-7:9-13, and the mass ratio of the ammonium persulfate aqueous solution to the mixed solution is 0.02-0.1:1.

[0019] The bionic mucus antifouling polymer prepared by the present invention is matched with the organosilicon coating and can form a dense dynamic gel layer at the interface between the organosilicon coating surface and the seawater when used in a seawater environment, thus having an antifouling effect.

[0020] Compared with the prior art, the invention comprises the following steps: firstly, mixing a dimethylaminoethyl methacrylate aqueous solution with a hydrogen peroxide aqueous solution, reacting the mixture under oil bath conditions to obtain TMAO; then dissolving an organic silicone ester polymer in dichloromethane to obtain an emulsion; then dissolving TMAO in methanol and dripping the mixture into the emulsion to obtain a mixed solution; finally, dripping an ammonium persulfate aqueous solution into the mixed solution, reacting the mixture under oil bath conditions to obtain a product, washing the mixture with water or methanol, centrifuging the mixture for 3-4 times, and drying the mixture to obtain a bionic mucus antifouling polymer; the bionic mucus antifouling polymer has the advantages of high synthetic stability, low cost, good antifouling performance, environmental friendliness, simple preparation method, low cost, and the like, and has great application potential in the field of marine antifouling. Description of the drawings:

[0021] Figure 1 It is the characteristic peak diagram of the precursor and TMAO involved in Example 1 of the present invention.

[0022] Figure 2 It is the characteristic peak diagram of the antifouling material, TMAO and product involved in Example 1 of the present invention.

[0023] Figure 3 This is a graph showing the anti-protein performance test results of the blank group, silicone group and product group prepared in Example 2 of the present invention.

[0024] Figure 4 This is a comparison chart of diatom attachment rates of the blank group, organic silicone grease group and product group prepared in Example 3 of the present invention. Specific implementation method:

[0025] The present invention will be further described below in conjunction with the accompanying drawings and in conjunction with specific implementation methods.

[0026] Embodiment 1:

[0027] The specific process of the method for preparing the biomimetic mucus antifouling polymer involved in this embodiment is as follows:

[0028] First, double-bond-containing silicone ester materials are connected through double-bond polymerization reaction to synthesize TMAO. Then, TMAO and silicone ester polymers are combined together through double bonds under heating conditions to synthesize bionic slime antifouling polymers.

[0029] (1) Preparation of TMAO

[0030] 8.1 g of 2-(dimethylamino)ethyl methacrylate was dissolved in 16.2 g of water and mixed evenly by rotating and vibrating on a vortex mixer to obtain a dimethylaminoethyl methacrylate aqueous solution;

[0031] Place 16 g of 30% by mass concentration hydrogen peroxide aqueous solution in a constant pressure dropping funnel;

[0032] The aqueous solution of dimethylaminoethyl methacrylate was placed in a three-necked flask equipped with a reflux condenser and a constant pressure dropping funnel filled with an aqueous hydrogen peroxide solution, and the aqueous hydrogen peroxide solution was slowly added dropwise, and an oil bath reaction was carried out at a temperature of 60°C for 6 hours;

[0033] After the reaction solution was cooled to room temperature, it was poured into a glass culture dish, placed in a refrigerator for 12 hours, and then placed in a freeze dryer for 12 hours to obtain TMAO;

[0034] (2) Preparation of biomimetic mucus antifouling polymer

[0035] After placing 12 g of organosilicon ester polymer in a beaker, add 17.4 g of dichloromethane and stir on a magnetic stirrer for 20 min. After forming an emulsion, transfer to a three-necked flask;

[0036] After placing 3 g of TMAO in another beaker, add 13.6 g of methanol, fully dissolve the organosilicon ester polymer by magnetic stirring, put it into a constant pressure dropping funnel, control the dropping speed, add it dropwise into the emulsion within 20 min and stir it thoroughly to obtain a mixed solution;

[0037] Place 2.48 g of 1% ammonium persulfate aqueous solution in a constant pressure dropping funnel placed on a three-necked flask, add dropwise to the mixed solution, and react in an oil bath at 60°C for 10-12 hours;

[0038] After the reaction liquid is cooled to room temperature, it is transferred to a centrifuge tube, 20 g of methanol is added dropwise to the reaction liquid to precipitate the product, and after washing with methanol and centrifuging 3-4 times, the product is transferred to a vacuum drying oven and dried at 60° C. for 48 hours to obtain a bionic mucus antifouling polymer.

[0039] The characteristic peaks of the precursor involved in this embodiment and TMAO are as follows Figure 1 As shown, the precursor is at 2775cm -1 and 2822cm -1 There are two characteristic peaks at 2775 cm-1, corresponding to the asymmetric and symmetric stretching vibrations of the tertiary amine group. -1 and 2822cm -1 The characteristic peak of the tertiary amine group disappears, and the peak at 2850cm -1 Existence (CH 3 ) 3 N + The stretching vibration peak of 2 O 2 During the oxidation process, the tertiary amine was successfully converted into tertiary amine nitrogen oxide, and TMAO was successfully synthesized.

[0040] The characteristic peaks of the antifouling material (prepared from biomimetic mucus antifouling polymer and silicone coating), TMAO and the product involved in this embodiment are as follows: Figure 2 As shown, 1735cm -1 The peak at 1635cm is the stretching vibration peak of C=O; -1 The peak at 1450cm is the stretching vibration peak of C=C; -1 CN + Stretching vibration peak; 1018cm -1 The symmetrical stretching vibration absorption peak of Si-O is at 809cm -1The appearance of Si-C stretching vibration peak at indicates that the product has been successfully synthesized.

[0041] Embodiment 2:

[0042] The specific process of the method for preparing the biomimetic mucus antifouling polymer involved in this embodiment is as follows:

[0043] (1) Preparation of TMAO

[0044] 9.1 g of N-[(3-(dimethylamino)propyl]methacrylamide was dissolved in 18 g of water and mixed evenly by rotating and vibrating on a vortex mixer to obtain a dimethylaminoethyl methacrylate aqueous solution;

[0045] Place 18.4 g of 30% by mass concentration hydrogen peroxide aqueous solution in a constant pressure dropping funnel;

[0046] The aqueous solution of dimethylaminoethyl methacrylate was placed in a three-necked flask equipped with a reflux condenser and a constant pressure dropping funnel filled with an aqueous hydrogen peroxide solution, and the aqueous hydrogen peroxide solution was slowly added dropwise, and an oil bath reaction was carried out at a temperature of 60°C for 6 hours;

[0047] After the reaction solution was cooled to room temperature, it was poured into a glass culture dish, placed in a refrigerator for 12 hours, and then placed in a freeze dryer for 12 hours to obtain TMAO;

[0048] (2) Preparation of biomimetic mucus antifouling polymer

[0049] After placing 12.1 g of organosilicon ester polymer in a beaker, add 14.3 g of dichloromethane and stir on a magnetic stirrer for 20 min. After forming an emulsion, transfer to a three-necked flask;

[0050] After placing 3.2 g of TMAO in another beaker, add 19.6 g of methanol, fully dissolve the organosilicon ester polymer by magnetic stirring, put it into a constant pressure dropping funnel, control the dropping speed, add it dropwise into the emulsion within 20 min and stir it thoroughly to obtain a mixed solution;

[0051] Place 4.2 g of 1% ammonium persulfate aqueous solution in a constant pressure dropping funnel placed on a three-necked flask, add dropwise to the mixed solution, and react in an oil bath at 60°C for 10-12 hours;

[0052] After the reaction liquid is cooled to room temperature, it is transferred to a centrifuge tube, 20 g of methanol is added dropwise to the reaction liquid to precipitate the product, and after washing with methanol and centrifuging 3-4 times, the product is transferred to a vacuum drying oven and dried at 60° C. for 48 hours to obtain a bionic mucus antifouling polymer.

[0053] The results of the protein resistance test of the product coating, the silicone coating and the blank coating in this example are as follows Figure 3 As shown, it can be seen that the anti-protein adsorption effect of the silicone ester group is not obvious, while the product group has an obvious anti-protein adsorption effect. This is because TMAO with anti-protein effect is grafted into the product.

[0054] Embodiment 3:

[0055] The specific process of the method for preparing the biomimetic mucus antifouling polymer involved in this embodiment is as follows:

[0056] (1) Preparation of TMAO

[0057] Dissolve 10.1 g of (2-dimethylaminoethyl) methacrylate in 20.2 g of water and mix well by rotating and vibrating on a vortex mixer to obtain a dimethylaminoethyl methacrylate aqueous solution;

[0058] Place 20.4 g of 30% by mass hydrogen peroxide aqueous solution in a constant pressure dropping funnel;

[0059] The aqueous solution of dimethylaminoethyl methacrylate was placed in a three-necked flask equipped with a reflux condenser and a constant pressure dropping funnel filled with an aqueous hydrogen peroxide solution, and the aqueous hydrogen peroxide solution was slowly added dropwise, and an oil bath reaction was carried out at a temperature of 60°C for 6 hours;

[0060] After the reaction solution was cooled to room temperature, it was poured into a glass culture dish, placed in a refrigerator for 12 hours, and then placed in a freeze dryer for 12 hours to obtain TMAO;

[0061] (2) Preparation of biomimetic mucus antifouling polymer

[0062] After placing 12.4 g of organosilicon ester polymer in a beaker, add 17.8 g of dichloromethane and stir on a magnetic stirrer for 20 min. After forming an emulsion, transfer to a three-necked flask;

[0063] After placing 3.3 g of TMAO in another beaker, add 20.9 g of methanol, fully dissolve the organosilicon ester polymer by magnetic stirring, put it into a constant pressure dropping funnel, control the dropping speed, add it dropwise into the emulsion within 20 min and stir it thoroughly to obtain a mixed solution;

[0064] Place 3.5 g of 1% ammonium persulfate aqueous solution in a constant pressure dropping funnel placed on a three-necked flask, add dropwise to the mixed solution, and react in an oil bath at 60°C for 10-12 hours;

[0065] After the reaction liquid is cooled to room temperature, it is transferred to a centrifuge tube, 20 g of methanol is added dropwise to the reaction liquid to precipitate the product, and after washing with methanol and centrifuging 3-4 times, the product is transferred to a vacuum drying oven and dried at 60° C. for 48 hours to obtain a bionic mucus antifouling polymer.

[0066] The results of the diatom attachment rate test on the product coating, the organosilicon coating and the blank coating in this example are as follows Figure 4 As shown, it can be seen that the diatom attachment rate of the product group is much lower than that of the blank group, and compared with the blank group, the diatom attachment rates of the four diatoms are all inhibited by more than 90%, indicating that the bionic mucus antifouling polymer has excellent anti-diatom adsorption performance.

Claims

1. A method for preparing a biomimetic mucus antifouling polymer, comprising: first, synthesizing trimethylamine nitroxide, and then grafting the trimethylamine nitroxide onto an organic silicone ester polymer by double bond polymerization to obtain a biomimetic mucus antifouling polymer; characterized in that: The specific process is: (1) Preparation of TMAO Dissolving the precursor in water and mixing evenly to obtain a dimethylaminoethyl methacrylate aqueous solution; The aqueous hydrogen peroxide solution is dropped into the aqueous dimethylaminoethyl methacrylate solution to carry out an oil bath reaction; The reaction solution is cooled to room temperature, frozen, and dried to obtain TMAO; (2) Preparation of biomimetic mucus antifouling polymer dissolving an organosilicone ester polymer in dichloromethane to obtain an emulsion; Dissolve TMAO in methanol and then drop it into the emulsion to obtain a mixed solution; Dropping an aqueous solution of ammonium persulfate into the mixed solution for oil bath reaction; After the reaction solution is cooled to room temperature, methanol is added dropwise to precipitate the product, which is then washed, centrifuged and dried to obtain a biomimetic mucus antifouling polymer.

2. The method for preparing the biomimetic mucus antifouling polymer according to claim 1, characterized in that: In step (1), the mass percentage concentration of the dimethylaminoethyl methacrylate aqueous solution is 30-40%.

3. The method for preparing the biomimetic mucus antifouling polymer according to claim 1, characterized in that: In step (1), the mass percentage concentration of the aqueous hydrogen peroxide solution is 30%, and the mass ratio of the aqueous dimethylaminoethyl methacrylate solution to the aqueous hydrogen peroxide solution is 3:

2.

4. The method for preparing the biomimetic mucus antifouling polymer according to claim 1, characterized in that: In step (1), the freezing time of the reaction solution is 12 hours, and the drying time is 12 hours.

5. The method for preparing the biomimetic mucus antifouling polymer according to claim 1, characterized in that: In step (1), the precursor includes 2-(dimethylamino)ethyl methacrylate, N-[(3-(dimethylamino)propyl]methacrylamide, and (2-dimethylaminoethyl)methacrylate.

6. The method for preparing the biomimetic mucus antifouling polymer according to claim 1, characterized in that: In step (2), the mass ratio of the organosilicon ester polymer to dichloromethane is 0.6-1, and the mass ratio of TMAO to methanol to emulsion is 1:4-7:9-13.

7. The method for preparing the biomimetic mucus antifouling polymer according to claim 1, characterized in that: In step (2), the mass percentage concentration of the ammonium persulfate aqueous solution is 1%, and the mass ratio of the ammonium persulfate aqueous solution to the mixed solution is 0.02-0.1:

1.

8. The method for preparing the biomimetic mucus antifouling polymer according to claim 1, characterized in that: In step (2), the product is washed with water or methanol, centrifuged 3-4 times, and then dried at 60° C. for 48 hours.

9. The method for preparing the biomimetic mucus antifouling polymer according to claim 1, characterized in that: In step (1), the temperature of the oil bath reaction is 60° C. and the time is 6 hours; in step (2), the temperature of the oil bath reaction is 60° C. and the time is 10-12 hours.

10. The method for preparing a biomimetic mucus antifouling polymer according to any one of claims 1 to 9, characterized in that: The bionic slime antifouling polymer is combined with the silicone coating and, when used in a seawater environment, can form a dynamic gel layer at the interface between the silicone coating surface and seawater.

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