A camptothecin-based fluorine-containing self-polishing antifouling resin and its preparation method and application

Abstract

The present invention provides a camptothecin-based fluorine-containing self-polishing antifouling resin, a preparation method thereof, and an application thereof. The self-polishing antifouling resin is formed by free radical copolymerization of at least a camptothecin-based methacrylate monomer, a methyl methacrylate monomer, a butyl acrylate monomer, a 2-methoxyethyl acrylate monomer, a hexafluorobutyl methacrylate monomer, and a triisopropylsilyl acrylate monomer under the action of an initiator. The camptothecin-based methacrylate monomer is polymerized by camptothecin and isocyanoethyl methacrylate in N,N-dimethylformamide. The present invention prepares a camptothecin-based methacrylate monomer for the first time, and then covalently bonds a camptothecin functional group to a fluorosilane methacrylate resin. Only a relatively low amount of camptothecin-based methacrylate monomer is required. The prepared self-polishing antifouling resin not only has antifouling properties but also has antibacterial properties, significantly reducing the amount of toxic antifouling agents used in antifouling coatings and reducing the preparation cost of antifouling coatings.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical materials, and in particular to a camptothecin-based fluorine-containing silane ester self-polishing antifouling resin, a preparation method thereof, and applications thereof. Background Art

[0002] The existence of the problem of marine fouling has brought great inconvenience to the development of marine resources and marine activities. Antifouling coatings are the most economical and effective way to prevent marine biological pollution. Among them, antifouling coatings based on self-polishing copolymers (SPCs), commonly known as side-group hydrolyzable acrylate copolymers, including silicon-based, copper-based or zinc-based acrylate copolymers, are the most commonly used because of their good performance, convenient construction process and good economy. Self-polishing antifouling coatings are usually divided into two parts: resin and antifouling agent. The base material of traditional self-polishing coatings is usually acrylic copolymers, including zinc acrylate, copper acrylate, silane acrylate, etc. The coating realizes surface self-polishing through the hydrolysis and release of the base resin, and continuously releases the internal antifouling agent to achieve antifouling. Antifouling agents usually include heavy metal antifouling agents and highly toxic organic antifouling agents. The use of these antifouling agents will threaten the marine ecology.

[0003] Patent publication number CN103289461A discloses the use of camptothecin and its derivatives as antifouling agents. Camptothecin exhibits high efficiency and broad-spectrum antifouling properties. However, this patent only uses camptothecin as an antifouling agent and does not covalently graft it to a resin segment for use as an antifouling base. Furthermore, the camptothecin and its derivatives are formulated with a resin to form an antifouling coating. Antifouling coatings typically use a non-polar solvent (xylene) in their formulation. Because camptothecin and its derivatives have poor solubility in non-polar solvents and tend to disperse unevenly, a large amount of antifouling agent is required to achieve an effective antifouling effect. Furthermore, the use of antifouling coatings on marine vessels requires a large amount of camptothecin antifouling agent, resulting in high costs.

[0004] In view of this, there is an urgent need for a self-polishing antifouling resin that can not only reduce the use of toxic antifouling agents in antifouling coatings, but also improve the uniformity of camptothecin distribution in the resin, and achieve a good antifouling effect at a lower content of camptothecin. Summary of the Invention

[0005] In view of this, the present invention aims to provide a camptothecin-based fluorine-containing self-polishing antifouling resin, its preparation method, and its application. This approach addresses the existing problem of reducing the use of toxic antifouling agents in antifouling coatings while also increasing the uniformity of camptothecin distribution in the resin, achieving excellent antifouling effects at relatively low camptothecin content.

[0006] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0007] A camptothecin-based fluorine-containing self-polishing antifouling resin is provided. The self-polishing antifouling resin is a camptothecin-based fluorosilane acrylate self-polishing antifouling resin, which is formed by free radical copolymerization of at least camptothecin methacrylate monomer, methyl methacrylate monomer, butyl acrylate monomer, 2-methoxyethyl acrylate monomer, hexafluorobutyl methacrylate monomer, and triisopropylsilyl acrylate monomer under the action of an initiator. The camptothecin methacrylate monomer is formed by polymerization of camptothecin and isocyanoethyl methacrylate in N,N-dimethylformamide.

[0008] In the present invention, camptothecin is dissolved in an N,N-dimethylformamide solvent, and camptothecin and isocyanoethyl methacrylate are uniformly polymerized in the N,N-dimethylformamide solvent to prepare a camptothecin-based methacrylate monomer for the first time. Then, the camptothecin functional group is covalently bonded to a fluorosilane methacrylate resin, and the camptothecin functional group is uniformly distributed in the self-polishing antifouling resin. The obtained self-polishing antifouling resin not only has significant antifouling properties, but also reduces the amount of toxic antifouling agents used in antifouling coatings. It also avoids the uneven mixing of camptothecin with the resin as a simple antifouling agent, which requires a large amount of antifouling agent and results in high preparation costs when used in antifouling coatings on ships. The self-polishing antifouling resin of the present invention also has antibacterial properties. In addition, due to the high polarity of the camptothecin side chain, the camptothecin-containing chain segments migrate to the coating surface and accumulate on the surface, thereby enhancing the antifouling effect of the coating.

[0009] In addition, the self-polishing antifouling optical resin of the present invention is antifouling in seawater through the camptothecin functional group; then the triisopropylsilane ester side chain of the polymer chain is hydrolyzed and falls off from the coating surface, accompanied by the slow release of the antifouling agent in the coating, thereby producing a smooth bottom surface of the ship, and effectively and long-term preventing the attachment of marine organisms to the bottom surface of the ship; the hexafluorobutyl methacrylate on the polymer chain reduces the surface energy of the polishing resin, thereby improving the antifouling and wear resistance of the coating.

[0010] Furthermore, the camptothecin methacrylate monomer accounts for about 0.1% to 1% of the total weight of the monomers.

[0011] In this setting, the self-polishing antifouling resin obtained at a relatively low content of camptothecin-based methacrylate monomer has significant antifouling properties, reducing the amount of toxic antifouling agents used in antifouling coatings. It also avoids the uneven mixing of camptothecin as an antifouling agent with the resin, which requires a large amount of antifouling agent and results in high preparation costs when used in antifouling coatings on ships.

[0012] Furthermore, the solvents used in the synthesis of the camptothecin-based fluorosilane acrylate self-polishing antifouling resin are N,N-dimethylformamide and xylene.

[0013] This setting enables the monomer with camptothecin functional group to have better solubility, and the monomer with camptothecin functional group can be more evenly combined with methacrylate fluorosilane resin, which not only makes the self-polishing antifouling resin antifouling, but also reduces the amount of camptothecin used and reduces the cost of reagent use.

[0014] Furthermore, the mass ratio of hexafluorobutyl methacrylate monomer to the total monomers is 5% to 20%, the mass ratio of methyl methacrylate monomer to butyl acrylate monomer is 65:35 to 55:45, the initiator accounts for 0.5% to 2% of the total monomers, the triisopropylsilyl acrylate monomer accounts for 10% to 20% of the total monomers, and the 2-methoxyethyl acrylate accounts for 1% to 4% of the total monomers.

[0015] Furthermore, the structural formula of the self-polishing antifouling resin is as follows:

[0016]

[0017] In the structural formula, a, b, c, d, e, and f are integers greater than 1.

[0018] Furthermore, the camptothecin methacrylate monomer has a structural formula as shown in Formula (II):

[0019]

[0020]

[0021] Furthermore, the reaction process for synthesizing camptothecin-based methacrylate monomer is as shown in formula (III):

[0022]

[0023] Furthermore, the reaction process of the antifouling resin is as shown in formula (IV):

[0024]

[0025] A method for preparing the self-polishing antifouling resin as described above comprises the following steps:

[0026] (1) preparing camptothecin-based methacrylate monomer;

[0027] At a temperature of 40° C., isocyanoethyl methacrylate and camptothecin were dissolved in N,N-dimethylformamide in a molar ratio of 1:1; the mixture was stirred at room temperature for 24 hours to obtain a camptothecin-based methacrylate monomer.

[0028] (2) mixing and dissolving camptothecin methacrylate monomer, methyl methacrylate monomer, butyl acrylate monomer, 2-methoxyethyl acrylate monomer, hexafluorobutyl methacrylate monomer, and triisopropylsilyl acrylate monomer in a mixed solution of N,N-dimethylformamide and xylene in a certain mass ratio to obtain solution A;

[0029] (3) Add N,N-dimethylformamide and xylene into a four-necked flask and heat to 85-90°C. Slowly add solution A dropwise in a protective gas environment. Stir continuously during the addition process at a stirring speed of 400-800 rpm. The addition is completed in 4 hours. After the addition is completed, maintain 90°C and continue the reaction for 2 hours to ensure sufficient reaction, thereby obtaining a self-polishing antifouling resin.

[0030] The preparation method is simple and has low preparation cost. The self-polishing antifouling resin obtained by the preparation method, which requires a low content of camptothecin-based methacrylate monomer, has antifouling performance and effectively reduces the use of toxic antifouling agents.

[0031] Furthermore, the mass ratio of xylene to N,N-dimethylformamide in step (2) is 10:1-5.

[0032] Furthermore, in step (3), the mass ratio of xylene to N,N-dimethylformamide is 10:0.5-4, and the mass ratio of N,N-dimethylformamide to camptothecin methacrylate monomer is (40-250):1.

[0033] Furthermore, the protective atmosphere in step (3) is one of nitrogen, argon or helium.

[0034] Furthermore, the dropping speed in step (3) is 50 to 90 g / h.

[0035] An application of the self-polishing antifouling resin as described above, and an application of the self-polishing antifouling resin in coatings.

[0036] Compared with the prior art, the camptothecin-based fluorine-containing self-polishing antifouling resin, its preparation method, and its application described in the present invention have the following advantages:

[0037] 1) In the present invention, camptothecin is dissolved in an N,N-dimethylformamide solvent, and camptothecin and isocyanoethyl methacrylate are uniformly polymerized in the N,N-dimethylformamide solvent, thereby preparing a camptothecin-based methacrylate monomer for the first time. The camptothecin functional group is then covalently bonded to a fluorosilane methacrylate resin, and the camptothecin functional group is uniformly distributed in the self-polishing antifouling resin. The resulting self-polishing antifouling resin has significant antifouling properties, reduces the amount of toxic antifouling agents used in antifouling coatings, and avoids the uneven mixing of camptothecin as an antifouling agent with the resin, which requires a large amount of antifouling agent and results in high preparation costs when used in antifouling coatings on ships. The self-polishing resin of the present invention also has antibacterial properties.

[0038] 2) The camptothecin-based methacrylate monomer of the present invention is prepared by a one-step reaction of camptothecin and methacrylic acid isocyanate. The preparation method is simple, easy to operate, and has low preparation cost;

[0039] 3) The self-polishing antifouling resin of the present invention has an antifouling effect in a seawater environment due to the camptothecin functional groups on the resin side chains. The triisopropylsilyl ester side chains of the polymer chain hydrolyze and fall off the coating surface. The antifouling agent in the coating is slowly released, thereby producing a smooth bottom surface of the ship and effectively and long-term preventing the attachment of marine organisms to the surface. The hydrolysis reaction formula of the resin is shown in FIG. Figure 1 .

[0040] 4) The camptothecin side chain of the present invention has a high polarity, and the camptothecin-containing chain segments will migrate to the surface of the coating and accumulate on the surface, thereby enhancing the antifouling effect of the coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a flow chart of the hydrolysis reaction of the self-polishing antifouling resin of the present invention;

[0042] Figure 2 This is a reaction flow chart for the synthesis of camptothecin-based methacrylate monomers of the present invention;

[0043] Figure 3 The reaction flow chart of the synthesis of the self-polishing antifouling resin of the present invention is as follows;

[0044] Figure 4 is the hydrogen nuclear magnetic resonance spectrum of the camptothecin methacrylate monomer of the present invention;

[0045] Figure 5 is a Fourier infrared image of the camptothecin methacrylate monomer of the present invention;

[0046] Figure 6 is a Fourier infrared image of the self-polishing antifouling resin of the present invention;

[0047] Figure 7This is a real sea hanging board picture of the self-polishing antifouling resin of Example 2 of the present invention at Dalipu Island in Xiamen, wherein Figure 7 (Left) The content of cuprous oxide in the coating formula is 20%. Figure 7 On the right, the cuprous oxide content in the coating formula is 40%;

[0048] Figure 8 This is a real sea hanging board map of Dalipu Island in Xiamen. It was immersed for half a year. The surface of the hanging board was not coated.

[0049] Figure 9 Statistical graph of the number of bacteria per unit area on the surface of the coatings prepared from the resins of Example 1, Example 4, and Comparative Example 1 after immersion for 3 days. DETAILED DESCRIPTION

[0050] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0051] Example 1

[0052] Synthesis of Camptothecin-Based Methacrylate

[0053] (1) Dissolve isocyanoethyl methacrylate (IEM) and camptothecin (DANTI) in dehydrated N,N-dimethylformamide at a molar ratio of 1:1 at 40°C. The concentration of IEM is 1 mol / L and the concentration of camptothecin is 0.1 mol / L. Mix well and stir at room temperature for 24 h.

[0054] (2) The reaction solution is placed in a low-temperature environment and the product CPT is purified by low-temperature crystallization. The low-temperature environment refers to the container being placed at a temperature less than 5°C after the reaction, preferably -5 to 0°C. Low-temperature crystallization is a conventional method that can be used to purify CPT.

[0055] 2. Synthesis of camptothecin-based fluorosilyl methacrylate self-polishing antifouling resin

[0056] (1) 132.5 g of methyl methacrylate, 70 g of butyl acrylate, 3 g of camptothecin-based methacrylate monomer, 30 g of hexafluorobutyl methacrylate, 10 g of 2-methoxyethyl acrylate, 50 g of triisopropylsilyl acrylate, and 4.5 g of azobisisobutyronitrile were dissolved in 60 g of xylene and N,N-dimethylformamide solution, wherein 30 g of xylene and 30 g of N,N-dimethylformamide were present.

[0057] (2) Add 325g of a mixed solvent of xylene and N,N-dimethylformamide into a 1L four-necked flask and heat it to 85°C. 200g of xylene and 125g of N,N-dimethylformamide are added dropwise in a nitrogen atmosphere. Stirring is continued during the addition process at a speed of 400rpm. The addition is completed within 4 hours. After the addition is completed, the temperature is maintained at 90°C and the reaction is continued for 2 hours to ensure sufficient reaction. After the reaction is completed, the product is exposed to air to terminate the reaction. A xylene solution of a camptothecin-based fluorosilicone acrylate self-polishing antifouling resin is obtained, which can be directly used to prepare antifouling coatings. The obtained resin is named CPTFR-1%.

[0058] Example 2

[0059] The difference between this embodiment and embodiment 1 is that the synthesis of camptothecin-based fluorosilane methacrylate self-polishing antifouling resin specifically includes the following steps:

[0060] (1) 132.5 g of methyl methacrylate, 70 g of butyl acrylate, 1.5 g of the camptothecin-based methacrylate monomer prepared in Example 1, 30 g of hexafluorobutyl methacrylate, 10 g of 2-methoxyethyl acrylate, 50 g of triisopropylsilyl acrylate, and 4.5 g of azobisisobutyronitrile were dissolved in 60 g of xylene and N,N-dimethylformamide solution, wherein 45 g of xylene and 15 g of N,N-dimethylformamide solution were used.

[0061] (2) Add 325g of a mixed solvent of xylene and N,N-dimethylformamide into a 1L four-necked flask and heat it to 90°C. The mixed solvent contains 245g of xylene and 80g of N,N-dimethylformamide. Add the mixed solution dropwise in a nitrogen atmosphere, stirring continuously during the addition process at a stirring speed of 500rpm, and complete the addition within 4 hours. After the addition is completed, maintain the temperature at 90°C and continue the reaction for 2 hours to ensure sufficient reaction. After the reaction is completed, expose the product to air to terminate the reaction. The obtained xylene solution of camptothecin-based fluorosilicone acrylate self-polishing antifouling resin can be directly used to prepare antifouling coatings. The obtained resin is named CPTFR-0.5%.

[0062] 3. The structural performance and actual sea antifouling performance of camptothecin-based methacrylate monomer and camptothecin-based methacrylate fluorosilane self-polishing antifouling resin were characterized. The resin with a camptothecin content of 0.5% was formulated into a coating with a copper content of 20% and 40%, respectively. The specific formulas are shown in Tables 1 and 2.

[0063] Table 1. Preparation method of camptothecin-based acrylic fluorine self-polishing antifouling coating containing 20% ​​copper

[0064] type Mass (g) Resin (mass calculated based on solid content) 240 Rosin liquid (mass calculated based on solid content) 180 Cuprous oxide 600 Mancozeb 150 Zinc pyrithione (ZnPT) 150 4,5-Dichloro-2-octyl-3-isothiazolinone (DCOIT) 60 Permanent red paste 60 Xylene solution of sodium polyamide (mass concentration 60%) 60 Xylene 90

[0065] Table 2. Preparation method of camptothecin-based acrylic fluorine self-polishing antifouling coating containing 40% copper

[0066] type Mass (g) Resin (mass calculated based on solid content) 320 Rosin liquid (mass calculated based on solid content) 240 Cuprous oxide 300 Mancozeb 200 Zinc pyrithione (ZnPT) 200 4,5-Dichloro-2-octyl-3-isothiazolinone (DCOIT) 80 Permanent red paste 80 Xylene solution of sodium polyamide (mass concentration 60%) 80 Xylene 90

[0067] Example 3

[0068] The difference between this embodiment and embodiment 1 is that the synthesis of the camptothecin-based fluorosilyl methacrylate self-polishing antifouling resin specifically includes the following steps.

[0069] (1) 132.5 g of methyl methacrylate, 70 g of butyl acrylate, 0.75 g of the camptothecin-based methacrylate monomer prepared in Example 1, 30 g of hexafluorobutyl methacrylate, 10 g of 2-methoxyethyl acrylate, 50 g of triisopropylsilyl acrylate, and 4.5 g of azobisisobutyronitrile were dissolved in 60 g of xylene and N,N-dimethylformamide solution, wherein 50 g of xylene and 10 g of N,N-dimethylformamide were used.

[0070] (2) Add 325g of a mixed solvent of xylene and N,N-dimethylformamide to a 1L four-necked flask and heat it to 90°C. 265g of xylene and 60g of N,N-dimethylformamide are added dropwise in a nitrogen atmosphere. Stirring is continued during the addition process at a speed of 400rpm. The addition is completed within 4 hours. After the addition is completed, the temperature is maintained at 90°C and the reaction is continued for 2 hours to ensure sufficient reaction. After the reaction is completed, the product is exposed to air to terminate the reaction. A xylene solution of a camptothecin-based fluorosilicone acrylate self-polishing antifouling resin is obtained, which can be directly used to prepare antifouling coatings. The obtained resin is named CPTFR-0.25%.

[0071] Example 4

[0072] The difference between this embodiment and embodiment 1 is that the synthesis of camptothecin-based fluorosilane methacrylate self-polishing antifouling resin specifically includes the following steps:

[0073] (1) 132.5 g of methyl methacrylate, 70 g of butyl acrylate, 0.3 g of the camptothecin-based methacrylate monomer prepared in Example 1, 30 g of hexafluorobutyl methacrylate, 10 g of 2-methoxyethyl acrylate, 50 g of triisopropylsilyl acrylate, and 4.5 g of azobisisobutyronitrile were dissolved in 60 g of xylene and N,N-dimethylformamide solution, wherein the xylene was 50 g and the N,N-dimethylformamide was 10 g.

[0074] (2) Add 325g of a mixed solvent of xylene and N,N-dimethylformamide to a 1L four-necked flask and heat it to 90°C. 250g of xylene and 75g of N,N-dimethylformamide are added dropwise in a nitrogen atmosphere. Stirring is continued during the addition process at a speed of 800rpm. The addition is completed within 4 hours. After the addition is completed, the temperature is maintained at 90°C and the reaction is continued for 2 hours to ensure sufficient reaction. After the reaction is completed, the product is exposed to air to terminate the reaction. A xylene solution of a camptothecin-based fluorosilicone acrylate self-polishing antifouling resin is obtained, which can be directly used to prepare antifouling coatings. The obtained resin is named CPTFR-0.1%.

[0075] Comparative Example 1

[0076] The difference between this comparative example and Example 1 is that the blank fluorosilane acrylate-based self-polishing antifouling resin without camptothecin is synthesized as follows:

[0077] (1) 132.5 g of methyl methacrylate, 70 g of butyl acrylate, 30 g of hexafluorobutyl methacrylate, 10 g of 2-methoxyethyl acrylate, 50 g of triisopropylsilyl acrylate, and 4.5 g of azobisisobutyronitrile were dissolved in 60 g of xylene solution.

[0078] (2) Add 325 g of xylene to a 1 L four-necked flask and heat to 90° C. Then, add the mixed solution dropwise in a nitrogen atmosphere while stirring continuously at 400 rpm. The addition is completed over 4 hours. After the addition is completed, the temperature is maintained at 90° C. and the reaction is continued for 2 hours to ensure sufficient reaction. After the reaction is completed, the product is exposed to air to terminate the reaction. The obtained xylene solution of camptothecin-based fluorosilyl acrylate self-polishing antifouling resin can be directly used to prepare antifouling coatings. The obtained resin is named CPTFR-0%.

[0079] Result Analysis

[0080] Figure 4 This is the H NMR spectrum of camptothecin methacrylate monomer, and the peak positions are as follows:

[0081] 1H NMR (400MHz, DMSO-d6) δ8.67 (s, 1H), 8.56–8.07 (m, 1H), 7.78 (d, J = 63.3Hz, 1H), 7. 32(s,1H),6.52(s,1H),5.73–5.14(m,2H),4.27(s,3H),1.84(s,1H),0.84(s,1H).

[0082] Figure 5 Fourier infrared test image of camptothecin methacrylate monomer: 3432cm -1 The peak at 2924 cm is the stretching vibration absorption peak of tertiary alcohol hydroxyl group.-1 The saturated CH stretching vibration absorption peak is at 2277 cm -1 The N=C=O stretching vibration absorption peak is at 3356 cm -1 and 1583cm -1 They represent the NH stretching vibration peak and NH bending vibration peak of -NHCOO- group, respectively, proving that camptothecin and ethyl isocyanate successfully reacted to prepare camptothecin-based methacrylate monomer.

[0083] Camptothecin methacrylate monomer with different contents was used as raw material to prepare camptothecin methacrylate fluorosilane self-polishing antifouling resin, wherein the contents of camptothecin methacrylate monomer were 0, 0.1%, 0.25%, 0.5% and 1% respectively. The test results are shown in FIG. Figure 6 , 2952cm -1 and 2870cm -1 The stretching vibration absorption peak of methyl group is at 1727cm -1 The stretching vibration peak of C=O is at 1633cm -1 and 3102cm -1 No peaks corresponding to C=C and CH stretching vibrations were found nearby, indicating that the double bond had reacted. -1 The peak is the characteristic peak of the amide carbonyl group of the camptothecin methacrylate monomer component.

[0084] The camptothecin-based methacrylate monomer content of 0.5% camptothecin-based fluorosilicone acrylate self-polishing antifouling resin was formulated into antifouling coatings containing 20% ​​and 40% cuprous oxide by mass, respectively. The antifouling coatings were tested on shallow waters around Dalipu Island in Xiamen. The test results are as follows: Figure 7 A six-month real sea hanging board test was conducted from November 2023 to May 2024. There was no obvious fouling on the coating surface, proving that the camptothecin-based methacrylate fluorosilane self-polishing antifouling resin has good antifouling performance. Even if the dosage of the toxic antifouling agent cuprous oxide is reduced, the antifouling paint can still have a good antifouling effect as a whole.

[0085] Depend on Figure 7 and Figure 8 It can be clearly seen that the self-polishing antifouling resin of the present invention has good antifouling properties.

[0086] Figure 9The CPTFR-0, CPTFR-0.1, and CPTFR-1 coatings were prepared according to the coating composition and mass shown in Table 2. For antibacterial testing of the coatings, Escherichia coli (a typical Gram-negative bacterium) and Staphylococcus aureus (a typical Gram-positive bacterium) were used as model bacteria to conduct a broad-spectrum bacterial adhesion inhibition test. Pseudoalteromonas marina (a typical marine bacterium) was selected to simulate the coating's ability to inhibit bacterial adhesion against marine bacteria. The specific testing steps are as follows:

[0087] (1) The polymer coating was evenly coated on the surface of a glass slide (area 19.76 cm2), dried, and then irradiated with a UV lamp (20 W, 253.7 nm) for 30 minutes to fully sterilize.

[0088] (2) The polymer coating was placed in a culture dish that had also been irradiated with UV light. 10 mL of Luria-Bertani (LB) liquid medium and a certain concentration of bacterial solution were added, and the addition ratio was adjusted to make the bacterial solution concentration 105-106 CFU / mL. The surface dish was then sealed with sealing film (with a breathing hole) and placed in a constant temperature incubator for 24 hours (24-36 hours for marine Pseudoalteromonas) and cultured at 37°C (the culture temperature for marine Pseudoalteromonas was set at 25°C).

[0089] (3) Place the culture dish in a culture dish sterilization barrel, dry-heat sterilize in an oven at 160°C for 4 hours, and cool in a clean bench. Pour hot solid culture medium into the culture dish, cool under ultraviolet light, turn it upside down, and seal it with sealing film for later use. Heat and sterilize the metal tweezers over the flame of an alcohol lamp and cool it. Then use tweezers to remove the sample piece from the culture dish after the culture is completed. Slowly rinse the coating surface with 20mL LB culture medium to remove the residual bacterial liquid. Then quickly rinse the coating with 10mL liquid culture medium. Then dilute the 10mL culture medium that has been rinsed on the surface to 103 times the original. Then take 10μL of the diluted solution and evenly apply it on the solid culture medium. After evenly spreading, place it in a constant temperature and light incubator at 37°C for 12 to 24 hours (25°C for marine Pseudomonas aeruginosa, 24 to 36 hours), and count. The number of bacteria on the coating surface is determined by plate counting method.

[0090] Bacteria are common primary fouling organisms, so antibacterial testing of coatings is important for evaluating their antifouling properties. The test results show that with the increase in camptothecin content, the antibacterial properties of the resin have been significantly improved. The number of Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa on the surface of CPTFR-0 resin without camptothecin was 1.3×10 5 , 1.6×10 5and 9.1×10 5 As the camptothecin content increased, the number of bacteria on the coating surface decreased. For CPTFR resin with a camptothecin content of 1% (CPTFR-1%), the number of Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa on the surface was 1.9×10 4 , 3.7×10 4 and 9.5×10 3 , which is one order of magnitude lower than that of CPTFR-0 surface. The experimental results show that camptothecin functional groups can effectively improve the antibacterial effect of the coating.

[0091] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope defined by the claims.

Claims

1. A camptothecin-based fluorine-containing self-polishing antifouling resin, characterized in that: The self-polishing antifouling resin is a camptothecin-based fluorosilane acrylate self-polishing antifouling resin, which is formed by free radical copolymerization of at least camptothecin methacrylate monomer, methyl methacrylate monomer, butyl acrylate monomer, 2-methoxyethyl acrylate monomer, hexafluorobutyl methacrylate monomer, and triisopropylsilyl acrylate monomer under the action of an initiator, wherein the camptothecin methacrylate monomer is formed by the reaction of camptothecin and isocyanoethyl methacrylate in N,N-dimethylformamide; the camptothecin methacrylate monomer accounts for 0.1% to 1% of the total mass of the monomers; the hexafluorobutyl methacrylate monomer accounts for 5% to 20% of the total mass of the monomers; the mass ratio of methyl methacrylate monomer to butyl acrylate monomer is 65:35 to 55:45; the initiator accounts for 0.5% to 2% of the total mass of the monomers; the triisopropylsilyl acrylate monomer accounts for 10 to 20% of the total mass of the monomers; and the 2-methoxyethyl acrylate accounts for 1 to 4% of the total mass of the monomers.

2. The self-polishing antifouling resin according to claim 1, characterized in that The solvents used in the synthesis of the camptothecin-based fluorosilane acrylate self-polishing antifouling resin are N,N-dimethylformamide and xylene.

3. The self-polishing antifouling resin according to claim 1, characterized in that The structural formula of the self-polishing antifouling resin is as follows: In the structural formula (I), a, b, c, d, e, and f are integers greater than 1.

4. The self-polishing antifouling resin according to claim 1, characterized in that The structural formula of the camptothecin methacrylate monomer is as follows:

5. The self-polishing antifouling resin according to claim 1, characterized in that The reaction process for the synthesis of camptothecin-based methacrylate monomer is shown in formula (III):

6. The self-polishing antifouling resin according to claim 1, characterized in that The reaction process of the antifouling resin is as shown in formula (IV):

7. A method for preparing a self-polishing antifouling resin according to any one of claims 1 to 6, characterized in that: The steps include: (1) preparing camptothecin-based methacrylate monomer; At a temperature of 40° C., isocyanoethyl methacrylate and camptothecin were dissolved in N,N-dimethylformamide in a molar ratio of 1:1; the mixture was stirred at room temperature for 24 hours to obtain a camptothecin-based methacrylate monomer. (2) mixing and dissolving camptothecin methacrylate monomer, methyl methacrylate monomer, butyl acrylate monomer, 2-methoxyethyl acrylate monomer, hexafluorobutyl methacrylate monomer, and triisopropylsilyl acrylate monomer in a mixed solution of N,N-dimethylformamide and xylene in a certain mass ratio to obtain solution A; (3) Add N,N-dimethylformamide and xylene into a four-necked flask and heat to 85-90°C. Slowly add solution A dropwise in a protective gas environment. Stir continuously during the addition process at a stirring speed of 400-800 rpm. The addition is completed in 4 hours. After the addition is completed, maintain 90°C and continue the reaction for 2 hours to ensure sufficient reaction, thereby obtaining a self-polishing antifouling resin.

8. Use of the self-polishing antifouling resin according to any one of claims 1 to 6, characterized in that: Application of the self-polishing antifouling resin in coatings.

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