Preparation method of capsaicin-fluorine modified polythiourethane marine antifouling coating

Abstract

The application discloses a preparation method of a capsaicin-fluorine modified polysulfur urethane marine antifouling coating, which comprises the following steps: adding isocyanate and capsaicin into a solvent and dispersing to obtain a pre-reaction liquid A, then adding dibutyl tin dilaurate to react and obtain the pre-reaction liquid A; adding isocyanate and perfluoro alcohol into the solvent and dispersing, then adding dibutyl tin dilaurate to react and obtain a pre-reaction liquid B; then weighing tetra (3-mercaptopropionic acid) pentaerythritol ester and adding into the pre-reaction liquid B, then continuously stirring to obtain a pre-reaction liquid C; adding the pre-reaction liquid A into the pre-reaction liquid C, then ultrasonic reacting to obtain a capsaicin-fluorine modified polysulfur urethane polymer; and coating the capsaicin-fluorine modified polysulfur urethane polymer on the surface of a substrate to obtain a capsaicin-fluorine modified polysulfur urethane antifouling coating. The capsaicin-fluorine modified polysulfur urethane marine antifouling coating can improve the static antifouling effect of the marine antifouling coating, and the coating has strong adhesion strength to the substrate, and can meet the long-term use requirement.

Description

Technical Field

[0001] This invention belongs to the field of antifouling coating technology, specifically relating to a method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating. Background Technology

[0002] Fouling organisms such as bacteria, algae, barnacles, and shellfish in the ocean can adhere to and grow on the surfaces of ships and other equipment submerged in seawater for extended periods. This leads to corrosion, increased fluid resistance, and consequently, higher fuel consumption and more frequent maintenance. Furthermore, these fouling organisms can be carried into other sea areas by ships, rapidly multiplying and causing invasive species invasions that severely disrupt the local ecological balance. Currently, 90% of marine antifouling coatings on the market achieve their effect by releasing toxic antifouling agents added to the coating to kill marine fouling organisms. The International Maritime Organization (IMO) has now completely banned the use of organotin marine antifouling coatings on commercial vessels; however, cuprous oxide, an organotin substitute, is banned in some countries and regions due to its harmful effects on the marine environment. Therefore, developing green, environmentally friendly, broad-spectrum, and highly effective marine antifouling coatings has become a research hotspot in the field of marine antifouling. This requires not only developing antifouling agents with good antifouling effects that are non-toxic and harmless, but also improving the adhesion strength of marine antifouling coatings to the substrate to meet the requirements of long-term use. Summary of the Invention

[0003] To address the aforementioned shortcomings, this invention discloses a method for preparing capsaicin-fluorine modified polysulfide urethane marine antifouling coating, which not only improves the static antifouling effect of the marine antifouling coating, but also gives the coating strong adhesion to the substrate, meeting the requirements for long-term use.

[0004] This invention is achieved using the following technical solution:

[0005] A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0006] (1) Weigh the following raw materials in parts by weight: 5-15 parts of isocyanate, 1-10 parts of capsaicin, and 10-20 parts of solvent; add isocyanate and capsaicin to the solvent under stirring to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0007] (2) Weigh the following raw materials in parts by weight: 10-20 parts of isocyanate, 5-15 parts of perfluorool, and 20-30 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0008] (3) Weigh 20 to 35 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue stirring the reaction for 30 min to obtain the pre-reaction solution C.

[0009] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by any one of spraying, brushing and dipping to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating.

[0010] Fluoropolymer antifouling coatings have low surface energy, resulting in weak adhesion of fouling organisms to the coating surface. These organisms can be removed by water shear force or mechanical removal without releasing any toxic antifouling agents. However, fluoropolymer antifouling coatings have poor static antifouling performance, while polysulfururethane contains numerous thioester and urethane bonds, exhibiting strong adhesion to the substrate but low air and water permeability. Therefore, this invention modifies polysulfururethane using capsaicin and perfluoroalcohols, grafting perfluoroalcohols as fluorinated segments onto the polysulfururethane side chains to reduce the material's surface energy. The material's low surface energy reduces the adhesion strength between fouling organisms and the material surface, allowing them to detach from the surface under the shear force of water flow or mechanical removal. Simultaneously, capsaicin segments act as side chains, imparting the original capsaicin properties to the material, exhibiting irritant and repellent effects on organisms, thus enhancing the static antifouling effect of the coating. Furthermore, the coating prepared from capsaicin-fluorinated modified polysulfururethane polymer exhibits strong adhesion strength to the substrate, ensuring long-term effective use in real-world environments.

[0011] Further, in step (1), isocyanate and capsaicin are added to the solvent under stirring conditions of 300-500 r / min to obtain mixture A.

[0012] Furthermore, in step (2), isocyanate and perfluoroalcohol are added to the solvent under stirring conditions of 300-500 r / min to obtain mixture B.

[0013] Furthermore, the stirring speed in step (3) is 300-500 r / min.

[0014] Furthermore, the temperature of the ultrasonic reaction in step (4) is 25–40°C.

[0015] Furthermore, the isocyanate is any one or more combinations of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, benzene diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate, and naphthalene diisocyanate; the perfluoroalcohol is any one or more combinations of 1H,1H,2H,2H-perfluoro-1-hexanol, 1H,1H,2H,2H-perfluoro-1-decanol, 1H,1H,2H,2H-perfluoro-1-dodecylol, and 1H,1H,2H,2H-perfluoro-1-octanol; and the solvent is any one or more combinations of ethyl acetate, methyl acetate, isoamyl acetate, cyclohexyl acetate, methyl propionate, acetone, and xylene.

[0016] Furthermore, the dry film thickness of the capsaicin-fluorine modified polysulfide antifouling coating is 200±20 μm.

[0017] Compared with existing technologies, this technical solution has the following advantages:

[0018] 1. This invention combines the hydrophobic properties of fluoropolymers with the pungent and irritating repellent properties of capsaicin to achieve a highly efficient and long-lasting antifouling effect. The coating is a green and environmentally friendly marine antifouling coating, and the resulting coating has great application prospects in the fields of ships and cages.

[0019] 2. The preparation method of the capsaicin-fluorine modified polysulfuron polymer of the present invention is simple to operate, low in cost, and suitable for large-scale production. Attached Figure Description

[0020] Figure 1 The results of measuring the capsaicin release rate under static conditions are the capsaicin-fluorine modified polysulfide antifouling coatings prepared according to the methods described in Examples 6 to 10 in Experimental Example 2. Curves 1 to 5 correspond to the antifouling coatings prepared according to the methods described in Examples 6, 7, 8, 9, and 10, respectively. Detailed Implementation

[0021] The present invention is further illustrated by the following examples, but these are not intended to limit the invention. Specific experimental conditions and methods not specified in the following examples are generally conventional methods well known to those skilled in the art.

[0022] Example 1: A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0023] (1) Weigh the following raw materials in parts by weight: 10 parts of isocyanate, 5 parts of capsaicin, and 15 parts of solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 400 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0024] (2) Weigh the following raw materials in parts by weight: 15 parts of isocyanate, 10 parts of perfluorool, and 25 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 400 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0025] (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 400 r / min for 30 min to obtain the pre-reaction solution C.

[0026] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 35℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by spraying to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 185 μm.

[0027] The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is ethyl acetate.

[0028] Example 2: A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0029] (1) Weigh the following raw materials in parts by weight: 8 parts of isocyanate, 4 parts of capsaicin, and 12 parts of solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 350 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0030] (2) Weigh the following raw materials in parts by weight: 12 parts of isocyanate, 8 parts of perfluorool, and 22 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 350 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0031] (3) Weigh 25 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 350 r / min for 30 min to obtain the pre-reaction solution C.

[0032] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 32℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by spraying to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 195 μm.

[0033] The isocyanate is a combination of toluene diisocyanate, phenyl diisocyanate and lysine diisocyanate; the perfluoroalcohol is a combination of 1H,1H,2H,2H-perfluoro-1-hexanol and 1H,1H,2H,2H-perfluoro-1-dodecyl alcohol; the solvent is a combination of ethyl acetate and isoamyl acetate.

[0034] Example 3: A method for preparing a capsaicin-fluorine modified polyurethane marine antifouling coating, comprising the following steps:

[0035] (1) Weigh the following raw materials in parts by weight: 12 parts of isocyanate, 8 parts of capsaicin, and 18 parts of solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 450 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0036] (2) Weigh the following raw materials in parts by weight: 18 parts of isocyanate, 12 parts of perfluorool, and 28 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 450 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0037] (3) Weigh 32 parts of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 450 r / min for 30 min to obtain the pre-reaction solution C.

[0038] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 38℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by dip coating to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 210 μm.

[0039] The isocyanate is isophorone diisocyanate; the perfluoroalcohol is a combination of 1H,1H,2H,2H-perfluoro-1-hexanol, 1H,1H,2H,2H-perfluoro-1-dodecyl alcohol and 1H,1H,2H,2H-perfluoro-1-octanol; the solvent is ethyl acetate.

[0040] Example 4: A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0041] (1) Weigh the following raw materials in the following proportions: 5 parts isocyanate, 1 part capsaicin, and 10 parts solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 300 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0042] (2) Weigh the following raw materials in parts by weight: 10 parts of isocyanate, 5 parts of perfluorool, and 20 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 300 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0043] (3) Weigh 20 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 300 r / min for 30 min to obtain the pre-reaction solution C.

[0044] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 25℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by any brushing method to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 180 μm.

[0045] The isocyanate is phenyl diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-dodecyl alcohol; and the solvent is acetone.

[0046] Example 5: A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0047] (1) Weigh the following raw materials in parts by weight: 15 parts of isocyanate, 10 parts of capsaicin, and 20 parts of solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 500 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0048] (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 15 parts of perfluorool, and 30 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 500 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0049] (3) Weigh 35 parts of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 500 r / min for 30 min to obtain the pre-reaction solution C.

[0050] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 40℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by brushing to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 220 μm.

[0051] The isocyanate is a combination of phenyl diisocyanate and lysine diisocyanate; the perfluoroalcohol is a combination of 1H,1H,2H,2H-perfluoro-1-hexanol and 1H,1H,2H,2H-perfluoro-1-octanol; and the solvent is a combination of ethyl acetate and methyl acetate.

[0052] Example 6: A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0053] (1) Weigh the following raw materials in the following proportions: 10 parts isocyanate, 7 parts capsaicin, and 20 parts solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 400 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0054] (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 10 parts of perfluorool, and 30 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 400 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0055] (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 400 r / min for 30 min to obtain the pre-reaction solution C.

[0056] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 35℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by brushing to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 190 μm.

[0057] The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is ethyl acetate.

[0058] Example 7: A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0059] (1) Weigh the following raw materials in parts by weight: 10 parts of isocyanate, 2 parts of capsaicin, and 20 parts of solvent; add the isocyanate and capsaicin to the solvent under stirring at a speed of 400 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0060] (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 10 parts of perfluorool, and 30 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 400 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0061] (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 400 r / min for 30 min to obtain the pre-reaction solution C.

[0062] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 35℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by brushing to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 195 μm.

[0063] The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is acetone.

[0064] Example 8: A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0065] (1) Weigh the following raw materials in the following proportions: 10 parts isocyanate, 5 parts capsaicin, and 20 parts solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 400 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0066] (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 10 parts of perfluorool, and 30 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 400 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0067] (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 400 r / min for 30 min to obtain the pre-reaction solution C.

[0068] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 32℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by brushing to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 210 μm.

[0069] The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is ethyl acetate.

[0070] Example 9: A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0071] (1) Weigh the following raw materials in the following proportions: 10 parts isocyanate, 7 parts capsaicin, and 20 parts solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 400 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0072] (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 12 parts of perfluorool, and 30 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 400 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0073] (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 400 r / min for 30 min to obtain the pre-reaction solution C.

[0074] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 36℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by brushing to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 205 μm.

[0075] The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is methyl propionate.

[0076] Example 10: A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, comprising the following steps:

[0077] (1) Weigh the following raw materials in parts by weight: 10 parts of isocyanate, 10 parts of capsaicin, and 20 parts of solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 400 r / min to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A;

[0078] (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 10 parts of perfluorool, and 30 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring at a speed of 400 r / min to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B;

[0079] (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue to stir the reaction at a speed of 400 r / min for 30 min to obtain the pre-reaction solution C.

[0080] (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W and the reaction temperature is 38℃. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by brushing to obtain capsaicin-fluorine modified polysulfide urethane antifouling coating. The dry film thickness of the coating is 215 μm.

[0081] The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is ethyl acetate.

[0082] Comparative Example 1: A method for preparing a polysulfide urethane antifouling coating, comprising weighing the following raw materials in parts by weight: 30 parts of hexamethylene diisocyanate, 30 parts of pentaerythritol tetrakis(3-mercaptopropionic acid) and 40 parts of ethyl acetate; dispersing hexamethylene diisocyanate and pentaerythritol tetrakis(3-mercaptopropionic acid) in ethyl acetate under stirring at 400 r / min to obtain mixture D; then adding 0.005% by weight of dibutyltin dilaurate of mixture D, and continuing to stir and react for 10 h to obtain a polysulfide urethane polymer; coating the polysulfide urethane polymer onto the surface of a substrate by brushing to prepare a polysulfide urethane antifouling coating with a dry film thickness of 200 μm.

[0083] Comparative Example 2: A method for preparing a fluorinated polysulfide urethane antifouling coating, comprising weighing the following raw materials in parts by weight: 30 parts hexamethylene diisocyanate, 10 parts 1H,1H,2H,2H-perfluoro-1-hexanol, and 40 parts ethyl acetate; dispersing the hexamethylene diisocyanate and 1H,1H,2H,2H-perfluoro-1-hexanol into ethyl acetate under stirring at 400 r / min to obtain mixture E; then adding 0.005% by weight of dibutyltin dilaurate to mixture E, and continuing stirring for 1 h to obtain a fluorinated side-chain pre-reaction solution; then weighing 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and slowly adding pentaerythritol tetrakis(3-mercaptopropionic acid) to the fluorinated side-chain pre-reaction solution, and continuing the reaction for 10 h. h, a fluorinated polysulfide urethane polymer was prepared, and the fluorinated polysulfide urethane polymer was coated onto the surface of the substrate by brushing to prepare a fluorinated polysulfide urethane antifouling coating with a dry film thickness of 200 μm.

[0084] Comparative Example 3: Dow Corning 184 standard silicone elastomer, a two-component kit product purchased from the market, was used. The basic components and curing agent were completely mixed at a weight ratio of 10:1 according to the instructions, and cured at 80 °C for 24 h to form a film. The dry film thickness of the coating was 200 μm.

[0085] Experimental Example 1: Antifouling coatings were prepared according to the methods described in Examples 1-10 and Comparative Examples 1-3, and the performance of the obtained antifouling coatings was tested as follows. The specific results are shown in Table 1:

[0086] (1) Bonding strength test: 20 mm aluminum ingots were bonded to the coating surface using epoxy adhesive, and the bonding strength between the coating and the substrate surface was measured using a digital pull-off adhesion tester.

[0087] (2) Elastic modulus test: Dumbbell-shaped specimens were prepared according to the standard procedure, with a diameter of ~1 mm, a width of 5 mm, and a length of 50 mm; 5 specimens were prepared for each polymer sample and grouped together; at room temperature, each group of test specimens was tested using a universal testing machine equipped with a 10 kN force sensor at a tensile rate of 5 mm / min, the test results of each group of specimens were recorded, and the average value was calculated as the test result;

[0088] (3) Contact angle and surface energy test: At room temperature, the contact angle and surface energy of the coating were tested before and after immersion in artificial seawater for 30 days. The static contact angle of the liquid on the coating surface was measured using a contact angle system (DSA25S). The test droplet volume was 2 μL. The test liquids used were deionized water and diiodomethane. Under the same conditions, the test was performed on each coating and the average contact angle was calculated. The surface energy of the coating was calculated using the Owens-Wendt-Rabel-Kaelble method.

[0089] Table 1. Performance test results of antifouling coatings prepared by different methods

[0090]

[0091] Experimental Example 2: A capsaicin-fluorine modified polysulfide urethane antifouling coating was prepared according to the methods described in Examples 6-10. The release rate of capsaicin in the coating under static conditions was then determined using a UV-Vis spectrophotometer. The results are shown in [reference needed]. Figure 1 The standard curve for capsaicin was prepared by first preparing 1.0 μg·L⁻¹ solutions. -1 2.5 μg·L -1 5.0 μg·L -1 7.5 μg·L -1 and 10.0 μg·L -1 Prepare capsaicin solution, and take 1 mL of each solution into a test tube, then add 2 mL of hydrochloric acid (0.5 mol·L⁻¹) to each tube. -1 ) and 1 mL containing NaNO2 (0.5 mol·L -1 ) and Na2MoO4 (0.025 mol·L -1 Prepare the colorimetric solution by shaking well and letting it stand for 15 min, then add 2 mL of NaOH (1.0 mol·L⁻¹). -1 Shake well and let stand for 30 min; measure the absorbance of the solution at a wavelength of 420 nm using a UV-Vis spectrophotometer (zero the solution if capsaicin is zero); plot the capsaicin standard curve with capsaicin concentration as the x-axis and absorbance value as the y-axis: y = 0.00059 + 0.01244x, R 2 =0.9997.

[0092] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for preparing a capsaicin-fluorine modified polysulfide urethane marine antifouling coating, characterized in that: Includes the following steps: (1) Weigh the following raw materials in parts by weight: 5-15 parts of isocyanate, 1-10 parts of capsaicin, and 10-20 parts of solvent; add isocyanate and capsaicin to the solvent under stirring to obtain mixture A, then add 0.005% of dibutyltin dilaurate by weight of mixture A, and then continue stirring for 30 min to obtain pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 10-20 parts of isocyanate, 5-15 parts of perfluorool, and 20-30 parts of solvent; add the isocyanate and perfluorool to the solvent under stirring to obtain mixture B, then add 0.005% of dibutyltin dilaurate by weight of mixture B, and then continue stirring for 30 min to obtain pre-reaction solution B; (3) Weigh 20 to 35 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) and add it to the pre-reaction solution B obtained in step (2). Then continue stirring the reaction for 30 min to obtain the pre-reaction solution C. (4) Add the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), and then sonicate for 60 min to obtain capsaicin-fluorine modified polysulfide urethane polymer. The ultrasonic power is 100 W. The capsaicin-fluorine modified polysulfide urethane polymer is used and coated on the surface of the substrate by any one of spraying, brushing and dipping to obtain capsaicin-fluorine modified polysulfide urethane marine antifouling coating. The isocyanate is any one or a combination of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, phenyl diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate, and naphthalene diisocyanate. The perfluorools are any one or a combination of 1H,1H,2H,2H-perfluoro-1-hexanol, 1H,1H,2H,2H-perfluoro-1-decanol, 1H,1H,2H,2H-perfluoro-1-dodecanol, and 1H,1H,2H,2H-perfluoro-1-octanol. The solvent is any one or a combination of ethyl acetate, methyl acetate, isoamyl acetate, cyclohexyl acetate, methyl propionate, acetone, and xylene.

2. The method for preparing the capsaicin-fluorine modified polysulfide urethane marine antifouling coating according to claim 1, characterized in that: In step (1), isocyanate and capsaicin are added to the solvent under stirring conditions of 300-500 r / min to obtain mixture A.

3. The method for preparing the capsaicin-fluorine modified polysulfide urethane marine antifouling coating according to claim 1, characterized in that: In step (2), isocyanate and perfluoroalcohol are added to the solvent under stirring conditions of 300-500 r / min to obtain mixture B.

4. The method for preparing the capsaicin-fluorine modified polysulfide urethane marine antifouling coating according to claim 1, characterized in that: The stirring speed in step (3) is 300-500 r / min.

5. The method for preparing the capsaicin-fluorine modified polysulfide urethane marine antifouling coating according to claim 1, characterized in that: The temperature of the ultrasonic reaction in step (4) is 25-40℃.

6. The method for preparing the capsaicin-fluorine modified polysulfide urethane marine antifouling coating according to claim 1, characterized in that: The dry film thickness of the capsaicin-fluorine modified polysulfide antifouling coating is 200±20 μm.

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