Preparation method of capsaicin-fluorine modified polythionocarbamate marine antifouling paint

Abstract

The invention discloses a preparation method of capsaicin-fluorine modified polythionocarbamate marine antifouling paint, which comprises the following steps: adding and dispersing isocyanate and capsaicin into a solvent, and then adding dibutyltin dilaurate for reaction to obtain a pre-reaction solution A; isocyanate and perfluoroalcohol are added and dispersed into a solvent, then dibutyltin dilaurate is added for a reaction, and a pre-reaction solution B is obtained; weighing pentaerythritol tetrakis (3-thiohydracrylate), adding the pentaerythritol tetrakis (3-thiohydracrylate) into the pre-reaction liquid B, and continuously stirring to react to obtain a pre-reaction liquid C; adding the pre-reaction liquid A into the pre-reaction liquid C, then carrying out ultrasonic reaction to obtain a capsaicin-fluorine modified polythionocarbamate polymer, and coating the surface of a substrate with the capsaicin-fluorine modified polythionocarbamate polymer to obtain the capsaicin-fluorine modified polythionocarbamate antifouling coating. According to the invention, the static antifouling effect of the marine antifouling paint can be improved, and the coating has relatively strong bonding strength on a substrate, so that the requirement of long-term use can be met.

Description

Technical Field

[0001] The invention belongs to the technical field of antifouling coatings, and in particular relates to a method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating. Background Art

[0002] Bacteria, algae, barnacles, shellfish and other fouling organisms in the ocean will adhere and grow on the surface of ships and other equipment that are immersed in seawater for a long time, causing corrosion and increased fluid resistance in ships and other marine equipment, which requires a large amount of fuel to be consumed and frequent maintenance. In addition, fouling organisms will enter other sea areas as the ship sails, and rapidly multiply and grow in large numbers, causing invasion of alien species, thereby seriously damaging the local ecological balance. At present, 90% of marine antifouling coatings on the market mainly kill marine fouling organisms by releasing toxic antifouling agents added to the coating to achieve the antifouling effect. Now, the International Maritime Organization (IMO) has completely banned the use of organotin marine antifouling coatings on commercial ships, but cuprous oxide, a substitute for organotin, is banned in some countries or regions because it is harmful to the marine environment. Therefore, the development of green, environmentally friendly, broad-spectrum and efficient marine antifouling coatings has become a research hotspot in the field of marine antifouling. In addition to the need to develop antifouling agents with good antifouling effects and non-toxic and harmless, it is also necessary to improve the bonding strength of marine antifouling coatings to the substrate to meet the requirements of long-term use. Summary of the invention

[0003] In view of the above-mentioned shortcomings, the present invention discloses a method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, which can not only improve the static antifouling effect of the marine antifouling coating, but also make the coating have a stronger bonding strength to the substrate, which can meet the requirements of long-term use.

[0004] The present invention is achieved by adopting the following technical solutions: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating comprises 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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 10-20 parts of isocyanate, 5-15 parts of perfluoroalcohol, and 20-30 parts of solvent; add the isocyanate and perfluoroalcohol to the solvent under stirring to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 20 to 35 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react for 30 minutes to obtain a pre-reaction solution C; (4) The pre-reaction liquid A obtained in step (2) is added to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W. The capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by any one of spraying, brushing and dipping to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating.

[0005] The surface of the fluoropolymer antifouling coating has a low surface energy, so that the adhesion strength of fouling organisms on the coating surface is relatively weak, and the fouling organisms can be removed only under the action of water shear force or mechanical removal, and no toxic antifouling agent materials need to be released. However, the static antifouling effect of the fluoropolymer antifouling coating is poor, and there are a large number of thioester bonds and urethane bonds inside the polythiourethane, which has a strong bonding strength with the substrate and low air permeability and water permeability. Therefore, the present invention uses capsaicin and perfluoroalcohol to modify the polythiourethane, and uses perfluoroalcohol as a fluorinated chain segment to graft onto the polythiourethane side chain to reduce the surface energy of the material. The lower surface energy of the material can reduce the bonding strength between fouling organisms and the material surface, and can detach the fouling organisms from the material surface under the action of water shear force or mechanical removal; at the same time, the capsaicin chain segment also serves as the side chain of the material, giving the material the original characteristics of capsaicin, which has a stimulating and repelling effect on organisms, thereby enhancing the static antifouling effect of the coating, and the coating prepared from capsaicin-fluorine-modified polythiourethane polymer has a strong bonding strength to the substrate, which can meet the long-term effective use in actual environments.

[0006] Furthermore, in step (1), isocyanate and capsaicin are dispersed in a solvent under stirring at a speed of 300 to 500 r / min to obtain a mixture A.

[0007] Furthermore, in step (2), isocyanate and perfluoroalcohol are dispersed in a solvent under stirring conditions at a speed of 300 to 500 r / min to obtain a mixture B.

[0008] Furthermore, the stirring speed in step (3) is 300 to 500 r / min.

[0009] Furthermore, the temperature of the ultrasonic reaction in step (4) is 25-40°C.

[0010] 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-dodecanol, 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.

[0011] Furthermore, the dry film thickness of the capsaicin-fluorine modified polythiourethane antifouling coating is 200±20 μm.

[0012] Compared with the prior art, this technical solution has the following beneficial effects: 1. The present invention combines the hydrophobicity of fluorine-containing polymers with the pungent and irritating repelling properties of capsaicin to achieve a highly efficient and long-lasting antifouling effect of the coating. The coating is a green and environmentally friendly marine antifouling coating. The obtained coating has great application prospects in the fields of ships, cages, etc.

[0013] 2. The preparation method of the capsaicin-fluorine modified polythiourethane polymer of the present invention is simple to operate, low in cost, and suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 These are the results of measuring the capsaicin release rate of the capsaicin-fluorine-modified polythiourethane antifouling coating prepared according to the method described in Examples 6 to 10 in Experimental Example 2 under static conditions, wherein curves 1 to 5 correspond to the antifouling coatings prepared by the methods described in Example 6, Example 7, Example 8, Example 9, and Example 10, respectively. DETAILED DESCRIPTION

[0015] The present invention is further described by the following examples, but is not intended to be limiting of the present invention. Specific experimental conditions and methods not specified in the following examples are conventional methods commonly known to those skilled in the art.

[0016] Example 1: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 15 parts of isocyanate, 10 parts of perfluoroalcohol, and 25 parts of solvent; add the isocyanate and perfluoroalcohol into the solvent under stirring at a speed of 400 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react at a speed of 400 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 35° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by spraying to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 185 μm; The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is ethyl acetate.

[0017] Example 2: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 12 parts of isocyanate, 8 parts of perfluoroalcohol, and 22 parts of solvent; add the isocyanate and perfluoroalcohol to the solvent under stirring at a speed of 350 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 25 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react at a speed of 350 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 32° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by spraying to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 195 μm; The isocyanate is a combination of toluene diisocyanate, phenylene diisocyanate and lysine diisocyanate; the perfluoroalcohol is a combination of 1H, 1H, 2H, 2H-perfluoro-1-hexanol and 1H, 1H, 2H, 2H-perfluoro-1-dodecanol; and the solvent is a combination of ethyl acetate and isoamyl acetate.

[0018] Example 3: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 18 parts of isocyanate, 12 parts of perfluoroalcohol, and 28 parts of solvent; add the isocyanate and perfluoroalcohol to the solvent under stirring at a speed of 450 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 32 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react at a speed of 450 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 38° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by dip coating to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 210 μm; The isocyanate is isophorone diisocyanate; the perfluoroalcohol is a combination of 1H, 1H, 2H, 2H-perfluoro-1-hexanol, 1H, 1H, 2H, 2H-perfluoro-1-dodecanol and 1H, 1H, 2H, 2H-perfluoro-1-octanol; and the solvent is ethyl acetate.

[0019] Example 4: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (1) Weigh the following raw materials in parts by weight: 5 parts of isocyanate, 1 part of capsaicin, and 10 parts of solvent; add isocyanate and capsaicin to the solvent under stirring at a speed of 300 r / min to obtain a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 10 parts of isocyanate, 5 parts of perfluoroalcohol, and 20 parts of solvent; add the isocyanate and perfluoroalcohol into the solvent under stirring at a speed of 300 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 20 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir the reaction at a speed of 300 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 25° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by any method such as brushing to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 180 μm; The isocyanate is benzene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-dodecanol; and the solvent is acetone.

[0020] Example 5: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 15 parts of perfluoroalcohol, and 30 parts of solvent; add the isocyanate and perfluoroalcohol into the solvent under stirring at a speed of 500 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 35 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir the reaction at a speed of 500 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 40° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by brushing to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 220 μm; The isocyanate is a combination of phenylene 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.

[0021] Example 6: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (1) Weigh the following raw materials in parts by weight: 10 parts of isocyanate, 7 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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 10 parts of perfluoroalcohol, and 30 parts of solvent; add the isocyanate and perfluoroalcohol to the solvent under stirring at a speed of 400 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react at a speed of 400 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 35° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by brushing to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 190 μm; The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is ethyl acetate.

[0022] Example 7: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (1) Weigh the following raw materials in parts by weight: 10 parts of isocyanate, 2 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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 10 parts of perfluoroalcohol, and 30 parts of solvent; add the isocyanate and perfluoroalcohol to the solvent under stirring at a speed of 400 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react at a speed of 400 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 35° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by brushing to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 195 μm; The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is acetone.

[0023] Example 8: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (1) Weigh the following raw materials in parts by weight: 10 parts of isocyanate, 5 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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 10 parts of perfluoroalcohol, and 30 parts of solvent; add the isocyanate and perfluoroalcohol to the solvent under stirring at a speed of 400 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react at a speed of 400 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 32° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by brushing to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 210 μm; The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is ethyl acetate.

[0024] Example 9: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (1) Weigh the following raw materials in parts by weight: 10 parts of isocyanate, 7 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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 12 parts of perfluoroalcohol, and 30 parts of solvent; add the isocyanate and perfluoroalcohol into the solvent under stirring at a speed of 400 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react at a speed of 400 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 36° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by brushing to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 205 μm; The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is methyl propionate.

[0025] Embodiment 10: A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, comprising the following steps: (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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 20 parts of isocyanate, 10 parts of perfluoroalcohol, and 30 parts of solvent; add the isocyanate and perfluoroalcohol to the solvent under stirring at a speed of 400 r / min to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 30 parts by weight of pentaerythritol tetrakis(3-mercaptopropionic acid) ester and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react at a speed of 400 r / min for 30 min to obtain a pre-reaction solution C; (4) adding the pre-reaction liquid A obtained in step (2) to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W and the reaction temperature is 38° C., and the capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by brushing to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 215 μm; The isocyanate is hexamethylene diisocyanate; the perfluoroalcohol is 1H,1H,2H,2H-perfluoro-1-hexanol; and the solvent is ethyl acetate.

[0026] Comparative Example 1: A method for preparing a polythiourethane antifouling coating, comprising weighing the following raw materials in parts by weight: 30 parts of hexamethylene diisocyanate, 30 parts of tetrakis(3-mercaptopropionic acid) pentaerythritol ester and 40 parts of ethyl acetate; adding hexamethylene diisocyanate and tetrakis(3-mercaptopropionic acid) pentaerythritol ester to ethyl acetate under a stirring condition of 400 r / min to obtain a mixture D, then adding 0.005% of dibutyltin dilaurate by weight of the mixture D, and continuing to stir and react for 10 h to obtain a polythiourethane polymer; and coating the polythiourethane polymer on the surface of a substrate by a brushing method to prepare a polythiourethane antifouling coating, wherein the coating has a dry film thickness of 200 μm.

[0027] Comparative Example 2: A method for preparing a fluorine-modified polythiourethane antifouling coating, which comprises weighing the following raw materials in parts by weight: 30 parts of hexamethylene diisocyanate, 10 parts of 1H,1H,2H,2H-perfluoro-1-hexanol and 40 parts of ethyl acetate; adding and dispersing the hexamethylene diisocyanate and 1H,1H,2H,2H-perfluoro-1-hexanol into ethyl acetate at a stirring speed of 400 r / min to obtain a mixture E, then adding 0.005% of dibutyltin dilaurate by weight of the mixture E, continuing to stir and react for 1 hour to obtain a fluorine-containing side chain pre-reaction liquid, and then weighing 30 parts by weight of tetrakis(3-mercaptopropionic acid) pentaerythritol ester, and slowly adding the tetrakis(3-mercaptopropionic acid) pentaerythritol ester to the fluorine-containing side chain pre-reaction liquid, and continuing to react for 10 h, preparing a fluorine-modified polythiourethane polymer, and coating the fluorine-modified polythiourethane polymer on the surface of a substrate by brushing to prepare a fluorine-modified polythiourethane antifouling coating, wherein the dry film thickness of the coating is 200 μm.

[0028] Comparative Example 3: Using a two-component kit product Dow Corning 184 standard silicone elastomer purchased from the market, the basic component and the curing agent were completely mixed in a weight ratio of 10:1 according to the instructions, and cured at 80°C for 24 hours to form a film. The dry film thickness of the coating was 200μm.

[0029] Experimental Example 1: An antifouling coating was prepared according to the methods described in Examples 1 to 10 and Comparative Examples 1 to 3, and the following performance tests were performed on the obtained antifouling coating. The specific results are shown in Table 1: (1) Bonding strength test: Use epoxy adhesive to bond a 20 mm aluminum ingot to the coating surface, and use a digital pull-off adhesion tester to measure the bonding strength between the coating and the substrate surface; (2) Elastic modulus test: dumbbell-shaped specimens with a diameter of ~1 mm, a width of 5 mm, and a length of 50 mm were prepared according to the standard procedure; 5 specimens were prepared for each polymer sample and used as a group; each group of test specimens was tested at room temperature 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 their average value was calculated as the test result; (3) Contact angle and surface energy test: At room temperature, the contact angle and surface energy of the coatings 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, and the liquids used in the test were deionized water and diiodomethane. Under the same conditions, each coating was tested and the average contact angle was calculated. The surface energy of the coating was calculated using the Owens-Wendt-Rabel-Kaelble method.

[0030] Table 1 Performance test results of antifouling coatings prepared by different methods

[0031] Experimental Example 2: A capsaicin-fluorine-modified polythiourethane antifouling coating was prepared according to the method described in Examples 6 to 10, and then the release rate of capsaicin in the coating under static conditions was measured using a UV-visible spectrophotometer. The measurement results are shown in Figure 1 ; The capsaicin standard curve was drawn by first preparing 1.0 μg·L -1 , 2.5 μg·L -1 , 5.0 μg·L -1 , 7.5 μg·L -1 and 10.0 μg·L -1 1 mL of capsaicin solution was taken from each tube and placed in a test tube. 2 mL of hydrochloric acid (0.5 mol·L -1 ) and 1 mL contained NaNO2 (0.5 mol·L -1 ) and Na2MoO4 (0.025 mol·L -1 ) color solution, shake well and let stand for 15 min, then add 2 mL of NaOH (1.0 mol·L -1 ) and shake well, let it stand for 30 min; use a UV-visible spectrophotometer to measure the absorbance of the solution at a wavelength of 420 nm (capsaicin is zero solution and adjusted to zero); use capsaicin concentration as the horizontal axis and absorbance value as the vertical axis to draw a capsaicin standard curve: y=0.00059+0.01244x, R 2 =0.9997.

[0032] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for preparing a capsaicin-fluorine modified polythiourethane marine antifouling coating, characterized in that: The following steps are involved: (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 a mixture A, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture A, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution A; (2) Weigh the following raw materials in parts by weight: 10-20 parts of isocyanate, 5-15 parts of perfluoroalcohol, and 20-30 parts of solvent; add the isocyanate and perfluoroalcohol to the solvent under stirring to obtain a mixture B, then add 0.005% of dibutyltin dilaurate based on the weight of the mixture B, and continue stirring and reacting for 30 minutes to obtain a pre-reaction solution B; (3) Weigh 20 to 35 parts by weight of pentaerythritol tetrakis(3-mercaptopropionate) and add it to the pre-reaction solution B obtained in step (2), and then continue to stir and react for 30 minutes to obtain a pre-reaction solution C; (4) The pre-reaction liquid A obtained in step (2) is added to the pre-reaction liquid C obtained in step (3), followed by ultrasonic reaction for 60 min to obtain a capsaicin-fluorine-modified polythiourethane polymer, wherein the ultrasonic power is 100 W. The capsaicin-fluorine-modified polythiourethane polymer is applied to the surface of a substrate by any one of spraying, brushing and dipping to obtain a capsaicin-fluorine-modified polythiourethane antifouling coating.

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

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

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

6. The method for preparing the capsaicin-fluorine modified polythiourethane marine antifouling coating according to claim 1, characterized in that: The isocyanate is any one or more combinations of hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, phenylene 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-dodecanol, 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.

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

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