Self-renewing temperature-sensitive antifouling paint and preparation method thereof

Abstract

The invention relates to a self-renewing temperature-sensitive antifouling paint and a preparation method thereof, belongs to the technical field of antifouling, and solves the problems that an antifouling paint for a marine environment in the prior art cannot simultaneously prevent and control algae growth and fouling organisms and is high in toxicity and easy to cause environmental damage. The invention provides a self-renewing temperature-sensitive antifouling paint. The antifouling paint comprises a component A and a component B, the component A comprises hydroxyl organic silicon resin, intelligent temperature-sensitive resin, degradable resin, a lubricant, a thixotropic agent and a first solvent; the component B comprises a curing agent, a catalyst and a second solvent. The antifouling paint can realize hydrophilic and hydrophobic automatic conversion in a range of 25-30 DEG C, further realizes control of fouling organisms and algae at the same time, and is good in control effect and free of pollution; the coating can be self-cleaned through degradation and self-updating, other stains easily attached to the surface of the ship body are removed, and effective protection of the ship body is achieved.

Description

Technical Field

[0001] The invention relates to the technical field of antifouling coatings, and in particular to a self-renewing temperature-sensitive antifouling coating and a preparation method thereof. Background Art

[0002] In the marine environment, some hulls or other equipment are immersed in the water environment for a long time, and fouling organisms (such as barnacles, etc.) are prone to attachment or massive reproduction of algae on the surface of the hull or equipment. The secretions of the above-mentioned organisms will corrode the protective layer on the surface of the hull or the hull itself, causing structural defects on the surface of the hull or a significant shortening of the service life.

[0003] At present, consumable antifouling coatings are generally used for biological control. Existing antifouling coatings mainly use a large amount of antifouling agents as biocides to effectively inhibit the attachment of fouling organisms to the surface of the hull. However, most antifouling agents are heavy metal compounds such as cuprous oxide, which are difficult to decompose in seawater and easily cause biological enrichment, destroying the ecological environment.

[0004] At present, some technical personnel at home and abroad have tried to develop fouling-releasing antifouling coatings based on the low surface energy and elastic characteristics of silicone materials. Although this type of coating has greatly reduced biological toxicity and can achieve a certain control effect on algae, it has a poor control effect on fouling organisms, especially when used on the surface of low-speed ships, the above defects are particularly obvious. Summary of the invention

[0005] In view of the above analysis, the embodiments of the present invention aim to provide a self-renewing temperature-sensitive antifouling coating and a preparation method thereof, so as to solve the problem that the existing antifouling coating cannot simultaneously prevent algae growth and fouling organisms and is highly toxic and easily causes environmental damage.

[0006] The present invention provides a self-renewing temperature-sensitive antifouling coating, which comprises component A and component B; component A comprises hydroxyl silicone resin, intelligent temperature-sensitive resin, degradable resin, lubricant, thixotropic agent and a first solvent; component B comprises a curing agent, a catalyst and a second solvent;

[0007] The preparation method of the intelligent temperature-sensitive resin is as follows: first, isopropyl acrylamide, hydroxy acrylate, azobisisobutyronitrile, and dimethylformamide are mixed and stirred to obtain a mixed monomer; the mixed monomer is added into xylene under heating conditions and kept warm for a period of time to obtain an intelligent temperature-sensitive resin process product; hydroxypropyl silicone oil is added into the process product, stirred evenly, and finally diisocyanate is slowly added, heated and kept warm to finally obtain the intelligent temperature-sensitive resin.

[0008] Specifically, the contents of the components in the component A are, by mass, 20 to 40 parts of hydroxy silicone resin, 10 to 20 parts of intelligent temperature-sensitive resin, 10 to 20 parts of degradable resin, 5 to 10 parts of lubricant, 0.5 to 1 part of thixotropic agent and 10 to 20 parts of the first solvent.

[0009] Specifically, the contents of the components in the component B are, by weight, 0.5 to 5 parts of curing agent, 0.1 to 0.5 parts of catalyst, and 5 to 10 parts of the second solvent.

[0010] Specifically, the hydroxy organic resin is polymethylsiloxane containing hydroxyl groups at both ends, with a viscosity of 1000 to 10000 cP and a structural formula of Where X is a positive integer.

[0011] Specifically, the preparation method of the intelligent temperature-sensitive resin is as follows:

[0012] S1: Add 50-70 parts of xylene to a three-necked flask, preheat the oil bath, mechanically stir, and control the oil temperature at 85-90°C; add 20-30 parts of isopropyl acrylamide, 5-15 parts of hydroxy acrylate, 1-2 parts of azobisisobutyronitrile, and 10-15 parts of dimethylformamide to a constant pressure dropping funnel, stir to dissolve, and disperse evenly to obtain a mixed monomer; increase the heating temperature of the oil bath, and start dripping the mixed monomer when the temperature of xylene in the three-necked flask rises to 90-95°C, and control the dripping time to 2-3 hours;

[0013] S2: After the addition is completed, the temperature is reduced to 80-85°C, and the reaction is kept warm for 2-3 hours. Then, 5-10 parts of hydroxypropyl silicone oil are added to the reactor, stirred, and mixed evenly. 10-20 parts of diisocyanate are slowly added to the reaction system. During the addition, the temperature is controlled at 80-85°C, and the addition time is controlled at 1-2 hours. After the addition is completed, the reaction is kept warm for 4-5 hours, and then cooled and discharged. The resulting resin solution is the intelligent temperature-sensitive resin.

[0014] Furthermore, the diisocyanate in step S2 is one or more of TDI, HDI, MDI, and IPDI; and the diisocyanate structure corresponds to the R group structure.

[0015] Specifically, the critical transition temperature of the smart thermosensitive resin is 25-30° C. When the temperature is lower than the critical transition temperature, the smart thermosensitive resin has a hydrophilic structure; when the temperature is higher than the critical transition temperature, the smart thermosensitive resin has a hydrophobic structure.

[0016] Specifically, the degradable resin in component A is one or more of polycaprolactone, polylactic acid, and polycaprolactone / lactide copolymer;

[0017] The lubricant is one or more of benzyl silicone oil, methyl silicone oil, and perfluoropolyether;

[0018] The thixotropic agent is one or more of polyamide wax, organic bentonite, and fumed silica;

[0019] The first solvent is one or more of xylene, butyl acetate, cyclohexanone, and ethyl acetate;

[0020] The curing agent in component B is one or more of ethyl silicate 28, ethyl silicate 32, and ethyl silicate 40;

[0021] The catalyst is one or more of stannous octoate and dibutyltin dilaurate;

[0022] The second solvent is one or more of xylene, butyl acetate, cyclohexanone and ethyl acetate.

[0023] The present invention also discloses a method for preparing the antifouling coating, which specifically comprises the following steps:

[0024] S21: Weigh or measure the raw materials of component A and component B according to the preset formula;

[0025] S22: preparing component A, adding hydroxy silicone resin, intelligent temperature-sensitive resin, degradable resin, lubricant and the first solvent into a dispersion cylinder, dispersing at high speed for ≥3 hours, then adding a thixotropic agent, continuing to disperse at high speed for ≥2 hours, and filtering out the material when the fineness of the coating drops below 80 μm to obtain component A;

[0026] S23: Prepare component B, add curing agent, catalyst and second solvent into a dispersion cylinder, disperse at high speed for 5 to 10 minutes, and discharge the material after the material is evenly dispersed to obtain component B.

[0027] The invention also discloses a method for using the antifouling coating, which comprises mixing component A and component B in a mass ratio of 10:1, stirring evenly and then carrying out construction; the construction process is one of brush coating, roller coating, high-pressure airless spraying and air spraying, and the coating thickness is 100 to 200 μm.

[0028] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0029] 1. The present invention creatively adds a brand-new intelligent temperature-sensitive resin and a degradable resin to the antifouling coating, so that the antifouling coating has the characteristics of intelligent temperature response and self-degradation and renewal, realizes the simultaneous prevention and control of fouling organisms and algae and the self-cleaning of the antifouling coating, and is environmentally friendly.

[0030] The preparation method of the intelligent temperature-sensitive resin is as follows: first, isopropyl acrylamide, hydroxy acrylate, azobisisobutyronitrile, and dimethylformamide are mixed and stirred to obtain a mixed monomer; the mixed monomer is added into xylene under heating conditions and kept warm for a period of time to obtain an intelligent temperature-sensitive resin process product; hydroxypropyl silicone oil is added into the process product, stirred evenly, and finally diisocyanate is slowly added, heated and kept warm to finally obtain the intelligent temperature-sensitive resin.

[0031] This kind of intelligent thermosensitive resin can realize intelligent temperature response and has a suitable critical transition temperature, which is 25-30°C; below the critical transition temperature, the intelligent thermosensitive resin is a hydrophilic / amphiphilic structure; above the critical transition temperature, the intelligent thermosensitive resin is a hydrophobic structure. The hydrophilic structure can inhibit the protein adhesion of fouling organisms, which is beneficial to avoid the attachment of fouling organisms, and the hydrophobic structure is beneficial to avoid the adhesion and growth of algae. During the operation of the ship, the temperature on the surface of the hull will change irregularly above and below the critical transition temperature, causing the hydrophilicity and hydrophobicity of the antifouling coating to change continuously, thereby achieving the simultaneous prevention and control of fouling organisms and algae. The static antifouling performance is excellent and environmentally friendly, and almost no toxic and harmful substances are produced.

[0032] In addition, due to the addition of degradable resin, the coating formed by the antifouling paint is always in a dynamic degradation and self-renewal state, further enhancing the static antifouling performance of the coating, so that some other difficult-to-remove stains remaining on the surface of the coating are removed as the coating self-renews.

[0033] 2. The present invention provides the coating with good coating performance and suitable self-renewal rate through reasonable component design, which can not only give full play to the antifouling performance of the intelligent temperature-sensitive resin, but also control the self-renewal rate of the antifouling coating within a suitable range, avoiding the need for repeated coating due to too fast self-renewal rate or the adhesion of stains due to too slow self-renewal rate, and the coating has moderate viscosity and can be coated by commonly used existing construction processes.

[0034] 3. The antifouling coating provided by the present invention has low surface energy (characteristics of silicone resin) and high elasticity, which helps to improve the static antifouling effect.

[0035] 4. The present invention provides a method for preparing an intelligent temperature-sensitive resin and a method for preparing and using the antifouling coating. The equipment and raw materials involved in the above method are easy to obtain, the operation difficulty is relatively low, and it is suitable for actual production and large-scale promotion.

[0036] In the present invention, the above-mentioned technical solutions can also be combined with each other to achieve more preferred combination solutions. Other features and advantages of the present invention will be described in the subsequent description, and some advantages can become obvious from the description, or can be understood by practicing the present invention. The purpose and other advantages of the present invention can be realized and obtained through the contents particularly pointed out in the description and the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The drawings are only for the purpose of illustrating particular embodiments and are not to be considered limiting of the present invention. Like reference symbols denote like components throughout the drawings.

[0038] Figure 1 It is a synthetic roadmap for intelligent temperature-sensitive resin;

[0039] Figure 2a This is a photograph of the seawater contact angle (76°) of the antifouling coating prepared in Example 1 at 20°C;

[0040] Figure 2b This is a photograph of the seawater contact angle (121°) of the antifouling coating prepared in Example 1 at 30°C;

[0041] Figure 3a This is a diagram showing the growth status of algae after the blank glass sheet in Example 1 was cultured at 20°C for one week;

[0042] Figure 3b This is a diagram showing the growth status of algae after the antifouling coated glass sheet in Example 1 was cultured at 20°C for one week;

[0043] Figure 3c This is a diagram showing the growth status of algae after the blank glass sheet in Example 1 was cultured at 30°C for one week;

[0044] Figure 3d This is a diagram showing the growth status of algae after the antifouling coated glass sheet in Example 1 was cultured at 30°C for one week;

[0045] Figure 4 This is a photo of a real sea hanging board of the antifouling coating prepared in Example 1 9 months ago. DETAILED DESCRIPTION

[0046] The preferred embodiments of the present invention are described in detail below in conjunction with the accompanying drawings, wherein the accompanying drawings constitute a part of this application and are used together with the embodiments of the present invention to illustrate the principles of the present invention, but are not used to limit the scope of the present invention.

[0047] The present invention provides a self-renewing temperature-sensitive antifouling coating, which comprises component A and component B; component A comprises hydroxyl silicone resin, intelligent temperature-sensitive resin, degradable resin, lubricant, thixotropic agent and a first solvent; component B comprises a curing agent, a catalyst and a second solvent;

[0048] The preparation method of the intelligent temperature-sensitive resin is as follows: first, isopropyl acrylamide, hydroxy acrylate, azobisisobutyronitrile, and dimethylformamide are mixed and stirred to obtain a mixed monomer; the mixed monomer is added to xylene under heating conditions and kept warm for a period of time to obtain an intelligent temperature-sensitive resin process product; hydroxypropyl silicone oil is added to the process product, stirred evenly, and finally diisocyanate is slowly added, heated and kept warm, and finally the intelligent temperature-sensitive resin is obtained;

[0049] The chemical structural formula of the intelligent temperature-sensitive resin is Where R is an aliphatic or aromatic group, R1 is Wherein m and n are positive integers.

[0050] The present invention creatively adds brand-new intelligent temperature-sensitive resin and degradable resin to the antifouling coating, so that the antifouling coating has the characteristics of intelligent temperature response and self-degradation and renewal, realizes the simultaneous prevention and control of fouling organisms and algae and self-cleaning of the antifouling coating, and is environmentally friendly.

[0051] Specifically, this kind of intelligent thermosensitive resin has a suitable critical transition temperature of 25 to 30°C, and can respond intelligently to the ambient temperature; below the critical transition temperature, the intelligent thermosensitive resin is a hydrophilic / amphiphilic structure; above the critical transition temperature, the intelligent thermosensitive resin is a hydrophobic structure. The hydrophilic structure can inhibit the protein adhesion of fouling organisms, which is beneficial to avoid the attachment of fouling organisms, and the hydrophobic structure is beneficial to avoid the adhesion and growth of algae. During the operation of the ship, the temperature on the surface of the hull will change irregularly above and below the critical transition temperature, causing the hydrophilicity and hydrophobicity of the antifouling coating to change continuously, thereby achieving the simultaneous prevention and control of fouling organisms and algae, excellent static antifouling performance and environmental friendliness, and almost no toxic and harmful substances are produced.

[0052] In addition, due to the addition of degradable resin, the coating formed by the antifouling paint is always in a dynamic degradation and self-renewal state, further enhancing the static antifouling performance of the coating, so that some other difficult-to-remove stains remaining on the surface of the coating are removed as the coating self-renews.

[0053] Specifically, the role and content of each component are determined as follows:

[0054] Hydroxy silicone resin: the main film-forming base, with certain low surface energy characteristics and excellent elasticity, which is conducive to static antifouling. Too high or too low content will damage the mechanical properties and antifouling properties of the coating.

[0055] Intelligent temperature-sensitive resin: It makes the antifouling coating have temperature-sensitive properties. The critical transition temperature is between 25-30℃. Below the critical transition temperature, the resin shows hydrophilicity, and above the critical transition temperature, the resin shows hydrophobicity. The hydrophilic and hydrophobic properties of the coating interface can be dynamically adjusted according to the changes in seawater temperature. Too high or too low a content will damage the mechanical properties and antifouling properties of the coating.

[0056] Degradable resin: It makes the antifouling paint / coating have the characteristics of self-degradation and renewal. It can be hydrolyzed in seawater, so that the coating is in a state of continuous surface self-renewal. Too low a content will cause the coating to be worn out too quickly and require repeated coating, which is not suitable for actual scenarios; too low a content will lead to reduced self-cleaning ability and accumulation of stubborn stains attached to the surface.

[0057] Lubricant: Lubricant mainly plays the role of small molecule mucus. By simulating the characteristics of mucus secreted by marine organisms, a mucus layer is produced on the surface to inhibit the attachment of fouling organisms. Too high or too low a content will affect the mechanical properties and anti-fouling properties of the coating.

[0058] Thixotropic agent: Thixotropic agent is used to adjust the viscosity and thixotropic properties of the coating. It is mainly used to improve the construction performance of the coating. Too high or too low content will affect the construction performance of the coating.

[0059] First solvent: The first solvent is mainly used to dissolve solvent resin, disperse the various components in the coating, adjust the viscosity of the coating, and improve the construction performance of the coating. Too high or too low content will affect the viscosity and construction performance of the coating.

[0060] Curing agent: reacts with hydroxy silicone resin to cure the resin. Too high or too low a concentration will affect the curing properties of the coating.

[0061] Catalyst: It regulates the curing rate. Too high or too low a catalyst will affect the curing rate of the coating.

[0062] Second solvent: The solvent is mainly used to dissolve solvent resin, disperse the various components in the coating, adjust the viscosity of the coating, and improve the construction performance of the coating. Too high or too low a content will affect the viscosity and construction performance of the coating.

[0063] Synergistic effect: By introducing temperature-responsive resin structures and degradable resin structures into low-surface-energy coatings, and utilizing the temperature-responsive characteristics of temperature-sensitive segments, the coating exhibits an amphiphilic structure under low-temperature conditions and transforms into a hydrophobic structure under high-temperature conditions, and utilizes the dynamic changes in surface hydrophilicity and hydrophobicity to achieve good static antifouling. At the same time, combined with the degradation characteristics of the degradable resin segments in the coating under the action of seawater, the surface self-renewal is achieved, further enhancing the static antifouling performance of the coating.

[0064] Specifically, the antifouling coating is prepared and stored in two components separately, so that the coating is easy to store and transport, and the resin is prevented from curing prematurely. Before use, component A and component B are mixed in a mass ratio of 10:1, and the antifouling coating is formed by a common coating or spraying process, which can be quickly cured and formed, and has an excellent antifouling effect.

[0065] Preferably, the contents of the components in the component A are, by mass, 20 to 40 parts of hydroxy silicone resin, 10 to 20 parts of intelligent temperature-sensitive resin, 10 to 20 parts of degradable resin, 5 to 10 parts of lubricant, 0.5 to 1 part of thixotropic agent and 10 to 20 parts of the first solvent.

[0066] Preferably, the contents of the components in the component B are, by mass, 0.5 to 5 parts of curing agent, 0.1 to 0.5 parts of catalyst, and 5 to 10 parts of the second solvent.

[0067] Specifically, the hydroxy organic resin is polymethylsiloxane containing hydroxyl groups at both ends, with a viscosity of 1000 to 10000 cP and a structural formula of Wherein X is a positive integer. The above silicone resin has the characteristics of low surface energy and high elasticity, which is beneficial to static antifouling. Hydroxyl silicone resin is mainly a resin base material, which plays the role of a film-forming material / film-forming base. The higher the viscosity, the higher the molecular weight. By adjusting the resin viscosity, the mechanical properties of the cured resin can be adjusted.

[0068] Specifically, the preparation method of the intelligent temperature-sensitive resin is as follows (the technical roadmap is as follows Figure 1 shown):

[0069] The preparation method of the intelligent temperature-sensitive resin is as follows: first, isopropyl acrylamide, hydroxy acrylate, azobisisobutyronitrile, and dimethylformamide are mixed and stirred to obtain a mixed monomer; the mixed monomer is added to xylene under heating conditions and kept warm for a period of time to obtain an intelligent temperature-sensitive resin process product; hydroxypropyl silicone oil is added to the process product, stirred evenly, and finally diisocyanate is slowly added, heated and kept warm, and finally the intelligent temperature-sensitive resin is obtained;

[0070] S1: Add 50-70 parts of xylene to a three-necked flask, preheat the oil bath, mechanically stir, and control the oil temperature at 85-90°C; add 20-30 parts of isopropyl acrylamide, 5-15 parts of hydroxy acrylate, 1-2 parts of azobisisobutyronitrile, and 10-15 parts of dimethylformamide to a constant pressure dropping funnel, stir to dissolve, and disperse evenly to obtain a mixed monomer; increase the heating temperature of the oil bath, and start dripping the mixed monomer when the temperature of xylene in the three-necked flask rises to 90-95°C, and control the dripping time to 2-3 hours;

[0071] S2: After the addition is completed, the temperature is reduced to 80-85°C, and the reaction is kept warm for 2-3 hours. Then, 5-10 parts of hydroxypropyl silicone oil are added to the reactor, stirred, and mixed evenly. 10-20 parts of diisocyanate are slowly added to the reaction system. During the addition, the temperature is controlled at 80-85°C, and the addition time is controlled at 1-2 hours. After the addition is completed, the reaction is kept warm for 4-5 hours, and then cooled and discharged. The resulting resin solution is the intelligent temperature-sensitive resin.

[0072] Furthermore, the diisocyanate in step S2 is one or more of TDI (toluene diisocyanate), HDI (hexamethylene diisocyanate), MDI (diphenylmethane diisocyanate), and IPDI (isophorone diisocyanate); and the diisocyanate structure corresponds to the R group structure.

[0073] Specifically, the critical transition temperature of the thermosensitive resin can be controlled by adjusting the ratio of isopropyl acrylamide, hydroxyacrylate and hydroxypropyl silicone oil. The intelligent thermosensitive resin prepared using the above parameters or process conditions has a critical transition temperature of 25 to 30°C, a molecular weight between 8000 and 12000, and a polydispersity index PDI of 1.2 to 1.6.

[0074] Specifically, the critical transition temperature of the smart thermosensitive resin is 25-30° C. When the temperature is lower than the critical transition temperature, the smart thermosensitive resin has a hydrophilic structure; when the temperature is higher than the critical transition temperature, the smart thermosensitive resin has a hydrophobic structure.

[0075] Specifically, the degradable resin in component A is one or more of polycaprolactone, polylactic acid, and polycaprolactone / lactide copolymer;

[0076] The lubricant is one or more of benzyl silicone oil, methyl silicone oil, and perfluoropolyether;

[0077] Preferably, the viscosity of the lubricant is 50 to 1000 cP. The lower the viscosity, the lower the molecular weight. The lubricant with a low molecular weight is more likely to seep out of the surface and have a good lubricating effect.

[0078] The thixotropic agent is one or more of polyamide wax, organic bentonite, and fumed silica;

[0079] The first solvent is one or more of xylene, butyl acetate, cyclohexanone, and ethyl acetate;

[0080] The curing agent in component B is one or more of ethyl silicate 28, ethyl silicate 32, and ethyl silicate 40;

[0081] The catalyst is one or more of stannous octoate and dibutyltin dilaurate;

[0082] The second solvent is one or more of xylene, butyl acetate, cyclohexanone and ethyl acetate.

[0083] The present invention also discloses a method for preparing the antifouling coating, which specifically comprises the following steps:

[0084] S21: Weigh or measure the raw materials of component A and component B according to the preset formula;

[0085] S22: preparing component A, adding hydroxy silicone resin, intelligent temperature-sensitive resin, degradable resin, lubricant and the first solvent into a dispersion cylinder, dispersing at high speed for ≥3 hours, then adding a thixotropic agent, continuing to disperse at high speed for ≥2 hours, and filtering out the material when the fineness of the coating drops below 80 μm to obtain component A;

[0086] S23: Prepare component B, add curing agent, catalyst and second solvent into a dispersion cylinder, disperse at high speed for 5 to 10 minutes, and discharge the material after the material is evenly dispersed to obtain component B.

[0087] Specifically, in step S22, a thixotropic agent is finally added to adjust the viscosity to a suitable range. The specific range can be determined based on practical experience and spraying process requirements. The viscosity itself has little effect on the temperature-sensitive properties of the coating and mainly affects the spraying performance.

[0088] Specifically, the time selection for high-speed dispersion is to make the coating reach the required fineness, generally the fineness of the topcoat can reach 80μm.

[0089] The present invention also discloses a method for using the antifouling coating, wherein component A and component B are blended at a mass ratio of 10:1, and construction can be performed after being stirred evenly. A too high or too low ratio is not conducive to the mechanical properties and antifouling effect of the coating.

[0090] The construction process is one of brush coating, roller coating, high-pressure airless spraying and air spraying, and the coating thickness is 100 to 200 μm.

[0091] Examples 1 to 3

[0092] The present invention is further illustrated by the following examples, in which the addition amounts of various substances are all in parts by mass.

[0093] Table 1 Summary of the names and addition amounts of the antifouling coating components in Examples 1 to 3

[0094]

[0095] The preparation method of the intelligent temperature-sensitive resin 1 in Example 1 is as follows:

[0096] Add 50 parts of xylene to a three-necked flask, heat in an oil bath, stir mechanically, and control the oil temperature at 85-90°C. Add 20 parts of isopropyl acrylamide, 5-15 parts of hydroxyethyl acrylate, 1 part of azobisisobutyronitrile, and 10 parts of dimethylformamide to a constant pressure dropping funnel, stir to dissolve, and disperse evenly. When the temperature of xylene in the three-necked flask rises to 90°C, start adding the mixed monomers dropwise, and control the dropping time to 2 hours.

[0097] After the addition is completed, the temperature is reduced to 80°C and the reaction is kept warm for 2 hours. Then, 5 parts of hydroxypropyl silicone oil are added to the reactor, stirred, and mixed evenly. 10 parts of hexamethylene diisocyanate are slowly added to the reaction system. The temperature is controlled at 80°C during the addition process. The addition time is 1 hour. After the addition is completed, the reaction is kept warm for 4 hours, and then cooled and discharged. The resulting resin solution is the intelligent temperature-sensitive resin 1. The critical transition temperature of the temperature-sensitive resin in seawater is 25°C, that is, it is hydrophilic below 25°C and hydrophobic above 25°C.

[0098] The preparation method of the intelligent temperature-sensitive resin 2 in Example 2 is as follows:

[0099] Add 60 parts of xylene to a three-necked flask, heat in an oil bath, stir mechanically, and control the oil temperature at 90°C. Add 25 parts of isopropyl acrylamide, 10 parts of hydroxypropyl acrylate, 2 parts of azobisisobutyronitrile, and 15 parts of dimethylformamide to a constant pressure dropping funnel, stir to dissolve, and disperse evenly. When the temperature of xylene in the three-necked flask rises to 90°C, start adding the mixed monomer dropwise, and control the dropping time to 2 hours.

[0100] After the addition is completed, the temperature is reduced to 80°C, and the reaction is kept warm for 2 hours. Then, 10 parts of hydroxypropyl silicone oil are added to the reactor, stirred, and mixed evenly, and 15 parts of toluene diisocyanate are slowly added to the reaction system, and the temperature is controlled at 85°C during the addition process, and the addition time is controlled at 2 hours. After the addition is completed, the reaction is kept warm for 4 hours, and then the material is cooled and discharged. The resulting resin solution is the thermosensitive resin 2, and the critical transition temperature of the thermosensitive resin in seawater is 27°C, that is, below 27°C, it is hydrophilic, and above 27°C, it is hydrophobic.

[0101] The preparation method of the intelligent temperature-sensitive resin 3 in Example 3 is as follows:

[0102] Add 70 parts of xylene to a three-necked flask, heat in an oil bath, stir mechanically, and control the oil temperature at 90°C. Add 30 parts of isopropyl acrylamide, 15 parts of hydroxyethyl acrylate, 2 parts of azobisisobutyronitrile, and 15 parts of dimethylformamide to a constant pressure dropping funnel, stir to dissolve, and disperse evenly. When the temperature of xylene in the three-necked flask rises to 90°C, start adding the mixed monomer dropwise, and control the dropping time to 3 hours.

[0103] After the addition is completed, the temperature is reduced to 80°C, and the reaction is kept warm for 2 hours. Then, 10 parts of hydroxypropyl silicone oil are added to the reactor, stirred, and mixed evenly, and 20 parts of isophorone diisocyanate are slowly added to the reaction system. The temperature is controlled at 85°C during the addition process, and the addition time is controlled at 2 hours. After the addition is completed, the reaction is kept warm for 4 hours, and then the material is cooled and discharged. The resulting resin solution is the intelligent temperature-sensitive resin 3, and the critical transition temperature of the temperature-sensitive resin in seawater is 29°C, that is, below 29°C, it is hydrophilic, and above 29°C, it is hydrophobic.

[0104] Contact angle test (Examples 1 to 3):

[0105] The contact angle of the prepared antifouling coating to seawater at 20°C and 30°C was tested respectively. The test data are as follows:

[0106] Example 1: As can be seen from Figure 2, the contact angle of the antifouling coating at 20°C is 76°, showing hydrophilic properties, and the contact angle of the coating at 30°C is 121°, showing hydrophobic properties, indicating that the prepared antifouling coating exhibits obvious temperature-sensitive properties.

[0107] Example 2: The contact angle of the antifouling coating at 20°C is 73°, showing hydrophilic properties, and the contact angle of the coating at 30°C is 118°

[0108] Example 3: The contact angle of the antifouling coating at 20°C is 77°, showing hydrophilic properties, and the contact angle of the coating at 30°C is 123°

[0109] Laboratory algae inhibition performance test (Examples 1 to 3):

[0110] The anti-algae performance of the prepared anti-fouling coating was tested under different temperature conditions. Taking Navicula as the experimental object, blank glass pieces and glass pieces coated with anti-fouling coating were added to the Navicula liquid, respectively, and cultured in a light incubator at temperatures set to 20°C and 30°C, respectively. After one week, the attachment of Navicula on the coating surface was observed under an inverted fluorescence microscope.

[0111] Under different temperature conditions, a large number of boat algae attached to the blank glass pieces. After one week of culture, no boat algae were observed on the glass pieces coated with the antifouling coating in Examples 1 to 3 in both the hydrophilic state (20°C) and the hydrophobic state (30°C), indicating that the self-renewing temperature-sensitive antifouling coating developed can inhibit the attachment of boat algae under different temperature conditions and has good antifouling performance. (The comparison of the algae inhibition performance in Example 1 is shown in Figure 3)

[0112] According to theoretical analysis, in the 30℃ test group, the algae control effect was mainly due to the combined effect of the hydrophobic properties, low surface energy properties and self-renewal properties of the antifouling coating; in the 20℃ test group, there was almost no contribution from the hydrophobic properties, and the algae control effect was mainly achieved by the synergistic effect of the low surface energy properties and self-renewal properties.

[0113] Real sea antifouling performance test:

[0114] The antifouling coating in Example 1 was used for a real sea hanging board test. The antifouling coating and the traditional fouling release type antifouling coating were coated on the left and right sides of the test ship board respectively, and a shallow sea hanging board test was carried out in Xiamen Dalipu Island to examine its comprehensive antifouling performance. The photos of the shallow sea hanging board after 9 months are shown in the figure. Figure 4 shown.

[0115] The left sample in the figure is a traditional fouling release antifouling coating without adding temperature responsive resin and degradation resin, and the right sample is a self-renewing temperature sensitive antifouling coating of the present invention. Figure 4 It can be seen from the figure that after 9 months of actual sea hanging, the antifouling coating developed by the present invention has no fouling organisms attached to the surface, and has good antifouling performance. However, the surface of the traditional fouling-releasing antifouling coating has a large number of algae and hard-shell fouling organisms attached, and the antifouling performance is poor.

[0116] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A self-renewing temperature-sensitive antifouling coating, characterized in that: The antifouling coating comprises component A and component B; component A comprises hydroxyl silicone resin, intelligent temperature-sensitive resin, degradable resin, lubricant, thixotropic agent and a first solvent; component B comprises a curing agent, a catalyst and a second solvent; The preparation method of the intelligent temperature-sensitive resin is as follows: firstly, isopropyl acrylamide, hydroxy acrylate, azobisisobutyronitrile and dimethylformamide are mixed and stirred to obtain a mixed monomer; the mixed monomer is added into xylene under heating conditions and kept warm for a period of time to obtain a process product of the intelligent temperature-sensitive resin; Hydroxypropyl silicone oil is added to the process product, stirred evenly, and finally diisocyanate is slowly added, heated and kept warm, to finally obtain the intelligent temperature-sensitive resin.

2. The antifouling coating according to claim 1, characterized in that: The contents of the components in the component A are, by mass, 20 to 40 parts of hydroxy silicone resin, 10 to 20 parts of intelligent temperature-sensitive resin, 10 to 20 parts of degradable resin, 5 to 10 parts of lubricant, 0.5 to 1 part of thixotropic agent and 10 to 20 parts of the first solvent.

3. The antifouling coating according to claim 1, characterized in that: The contents of the components in the component B are, by weight, 0.5 to 5 parts of curing agent, 0.1 to 0.5 parts of catalyst, and 5 to 10 parts of the second solvent.

4. The antifouling coating according to claim 1, characterized in that: The hydroxy organic resin is a polymethylsiloxane containing hydroxyl groups at both ends, with a viscosity of 1000 to 10000 cP and a structural formula of Where X is a positive integer.

5. The antifouling coating according to claim 1, characterized in that: The preparation method of the intelligent temperature-sensitive resin is as follows: S1: Add 50-70 parts of xylene to a three-necked flask, preheat the oil bath, mechanically stir, and control the oil temperature at 85-90°C; add 20-30 parts of isopropyl acrylamide, 5-15 parts of hydroxy acrylate, 1-2 parts of azobisisobutyronitrile, and 10-15 parts of dimethylformamide to a constant pressure dropping funnel, stir to dissolve, and disperse evenly to obtain a mixed monomer; increase the heating temperature of the oil bath, and start dripping the mixed monomer when the temperature of xylene in the three-necked flask rises to 90-95°C, and control the dripping time to 2-3 hours; S2: After the addition is completed, the temperature drops to 80-85°C, and the reaction is kept warm for 2-3 hours. Then, 5-10 parts of hydroxypropyl silicone oil are added to the reactor, stirred, and mixed evenly. 10-20 parts of diisocyanate are slowly added to the reaction system. The temperature is controlled at 80-85°C during the addition process, and the addition time is controlled at 1-2 hours. After the addition is completed, the reaction is kept warm for 4-5 hours, and then cooled and discharged. The obtained resin solution is the intelligent temperature-sensitive resin.

6. The antifouling coating according to claim 5, characterized in that: The diisocyanate in step S2 is one or more of TDI, HDI, MDI, and IPDI; the diisocyanate structure corresponds to the R group structure.

7. The antifouling coating according to claim 1, characterized in that: The critical transition temperature of the intelligent thermosensitive resin is 25-30° C. When the temperature is lower than the critical transition temperature, the intelligent thermosensitive resin has a hydrophilic structure; when the temperature is higher than the critical transition temperature, the intelligent thermosensitive resin has a hydrophobic structure.

8. The antifouling coating according to claim 1, characterized in that: The degradable resin in component A is one or more of polycaprolactone, polylactic acid, and polycaprolactone / lactide copolymer; The lubricant is one or more of benzyl silicone oil, methyl silicone oil, and perfluoropolyether; The thixotropic agent is one or more of polyamide wax, organic bentonite, and fumed silica; The first solvent is one or more of xylene, butyl acetate, cyclohexanone, and ethyl acetate; The curing agent in component B is one or more of ethyl silicate 28, ethyl silicate 32, and ethyl silicate 40; The catalyst is one or more of stannous octoate and dibutyltin dilaurate; The second solvent is one or more of xylene, butyl acetate, cyclohexanone and ethyl acetate.

9. A method for preparing the antifouling coating according to any one of claims 1 to 8, characterized in that: The specific steps include: S21: Weigh or measure the raw materials of component A and component B according to the preset formula; S22: preparing component A, adding hydroxy silicone resin, intelligent temperature-sensitive resin, degradable resin, lubricant and the first solvent into a dispersion cylinder, dispersing at high speed for ≥3 hours, then adding a thixotropic agent, continuing to disperse at high speed for ≥2 hours, and filtering out the material when the fineness of the coating drops below 80 μm to obtain component A; S23: Prepare component B, add curing agent, catalyst and second solvent into a dispersion cylinder, disperse at high speed for 5 to 10 minutes, and discharge the material after the material is evenly dispersed to obtain component B.

10. A method for using the antifouling coating according to any one of claims 1 to 8 or the antifouling coating prepared by the preparation method according to claim 9, characterized in that: Component A and component B are mixed in a mass ratio of 10:1, and construction can be carried out after stirring evenly; the construction process is one of brush coating, roller coating, high-pressure airless spraying, and air spraying, and the coating thickness is 100 to 200 μm.

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