CN115851110B - Preparation method of light response long-acting super-lubricating anti-fouling paint based on coumarin - Google Patents
Preparation method of light response long-acting super-lubricating anti-fouling paint based on coumarin Download PDFInfo
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Abstract
The invention discloses a preparation method of a coumarin-based light response long-acting super-lubricating antifouling paint. The prepared biscoumarin end group polydimethylsiloxane lubricating liquid is treated by 365nm ultraviolet in the preparation process, and coumarin groups of the end groups are connected with coumarin in the coumarin modified organosilicon polyurethane main body in a reversible covalent bond mode through photodimerization, so that the biscoumarin end group polydimethylsiloxane lubricating liquid is combined in the coumarin modified organosilicon polyurethane main body in the reversible covalent bond mode, the loss of the lubricating liquid under the flushing of seawater is effectively reduced, and the problems that the lubricating liquid of a super-lubricating coating injected by the traditional lubricating liquid is easy to lose and the service life is short are solved. According to the invention, the activity of the end group of the biscoumarin end group polydimethylsiloxane lubricating liquid on the surface of the coumarin modified organosilicon polyurethane main body is regulated and controlled by utilizing the light response reversible dimerization behavior of the coumarin compound, so that the surface lubricating property is regulated, the coating can regulate the antifouling strength according to different fouling strengths in the daytime and at night, the light response is as required, and the antifouling efficiency is effectively improved.
Description
Technical Field
The invention relates to a marine antifouling paint technology, in particular to a coumarin-based light response long-acting super-lubricating antifouling paint and a preparation method thereof.
Background
With the development of the national strategy of ocean, shallow sea equipment such as underwater robots, unmanned submarines, ocean buoy workstations and the like show great application potential in the fields of scientific research, economy and the like. However, marine equipment is easy to be stained by marine organisms when running in a marine environment, and has great influence on the production and life of human beings, so that huge economic loss is caused. The simplest and most effective method to solve the marine biofouling problem is to apply marine antifouling paint.
The international maritime organization has prohibited the use of nondegradable, teratogenic tributyltin self-polishing antifouling paints worldwide from month 1 in 2008, so environmental protection low surface energy antifouling paints have received a great deal of attention. The injection of lubricating liquids into porous super-lubricated surfaces (SLIPS-infusedporous surface) has attracted continued attention due to the low surface energy, low young's modulus and dynamic super-lubricated surfaces. The injected lubricating liquid forms a dynamic lubrication layer that can significantly reduce the attachment of biofouling compared to conventional low surface energy coatings. However, the injected lubricating liquid is easy to run off, the antifouling performance is reduced, and the long-acting service life of the super-lubricating coating in the actual sea area is shortened. In addition, the traditional marine antifouling paint has only a single antifouling mode and can not meet the requirements of different occasions and time. Therefore, the injected lubricating liquid is not easy to run off, the water flow scouring of marine environment is resistant, and the responsive long-acting super-lubricating anti-fouling paint capable of responding to environmental stimulus and adjusting the anti-fouling performance of the super-lubricating coating as required has great research potential.
Disclosure of Invention
The invention aims to solve the problem of shortened service life caused by easy loss of lubricating liquid of the traditional lubricating liquid injection type super-lubricating antifouling paint, and provides a preparation method of the light-responsive long-acting super-lubricating antifouling paint based on coumarin for overcoming the defects of the prior art.
In order to solve the technical problem, the solution of the invention comprises the following steps:
(1) Mixing 1-100 parts by weight of monohydroxy coumarin compound, 10-1000 parts by weight of epichlorohydrin, 0.1-10 parts by weight of potassium hydroxide and 10-1000 parts by weight of solvent alpha, and stirring at 50-100 ℃ for 1-10 hours. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the epoxy coumarin compound.
(2) Mixing 1-100 parts by weight of the epoxy coumarin compound prepared in the step (1), 10-1000 parts by weight of the double aminopropyl end group reactive polydimethylsiloxane and 10-1000 parts by weight of the solvent beta, and stirring the mixture at 50-100 ℃ for 1-5 hours. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the biscoumarin end group polydimethylsiloxane lubricating liquid.
(3) 10-1000 parts by weight of double-end-group reactive polydimethylsiloxane, 1-100 parts by weight of polyisocyanate, 10-1000 parts by weight of solvent beta, 1-50 parts by weight of dihydroxycoumarin compound and 1-50 parts by weight of polyol or polyamine are mixed, and the mixture is heated for 1-4 hours in a nitrogen atmosphere at 60-80 ℃ to form coumarin modified organic silicon polyurethane feed liquid.
(4) And (3) continuously adding 1-30 parts by weight of the prepared biscoumarin end group polydimethylsiloxane lubricating liquid (2) into the coumarin modified organosilicon polyurethane liquid (3), dispersing and uniformly mixing, and then radiating with 365nm ultraviolet light and stirring for 1-4 hours to obtain the coumarin-based light response long-acting super-lubrication anti-fouling paint.
In the invention, the monohydroxy coumarin compound refers to: a composition of one or more of 4-methylumbelliferone, 5-methylumbelliferone, 3-hydroxycoumarin, 4-hydroxycoumarin, 6-hydroxycoumarin and 7-hydroxycoumarin.
In the invention, the weight average molecular weight of the double aminopropyl end group reactive polydimethylsiloxane is 1000-10000.
In the invention, the weight average molecular weight of the double-end-group reactive polydimethylsiloxane is 1000-10000; the double end group in the formula refers to: one or more of hydroxypropyl, aminopropyl, and epoxy groups.
In the present invention, the polyisocyanate is a diisocyanate or triisocyanate, specifically: one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and triphenylmethane triisocyanate.
In the present invention, the dihydroxycoumarin compound means: a composition of one or more of 4, 7-dihydroxycoumarin, 5, 7-dihydroxycoumarin, 6, 7-dihydroxycoumarin, 5, 7-dihydroxy-4-methylcoumarin, 7, 8-dihydroxy-4-methylcoumarin, 7-dihydroxypropyl-4-methylcoumarin, and 7-dihydroxybutyl-4-methylcoumarin.
In the present invention, the polyol or polyamine cross-linking agent means: one or more of glycerol, butanediol, triethylamine and hexamethylenediamine.
In the present invention, the solvent α means: one or more of water, methanol, ethanol, N-dimethylformamide.
In the present invention, the solvent β means: one or more of tetrahydrofuran, xylene, N-dimethylformamide, ethyl acetate and butyl acetate.
The application method of the coumarin-based light response long-acting super-lubricating antifouling paint comprises the following steps:
uniformly coating the antifouling paint on the surface to be sprayed in an air spraying mode, wherein the coating thickness of a wet film is 100-1000 mu m; drying under the condition of room temperature of ventilation drying to obtain a dry coating film.
The principle of the invention is described as follows:
coumarin and derivatives thereof have response to ultraviolet light, and double bonds on a pyran ring of the coumarin can form butane rings under the action of 365nm ultraviolet light, so that 2 coumarin monomers form a dimeric compound under the action of covalent bonds; the covalent bond breaks under the action of 254nm ultraviolet rays to reform 2 independent coumarin monomers, namely photodimerization and photodepolymerization of coumarin response to ultraviolet rays.
Based on photodimerization and photolysis polymerization of coumarin under different ultraviolet rays, the biscoumarin end group polydimethylsiloxane lubricating liquid is synthesized, and the biscoumarin end group polydimethylsiloxane lubricating liquid is blended and injected into coumarin modified organosilicon polyurethane to construct the light response long-acting super-lubrication anti-fouling paint based on coumarin.
Under 365nm ultraviolet irradiation treatment in the preparation process of the biscoumarin end-group polydimethylsiloxane lubricating liquid, coumarin groups of the end groups are connected with coumarin in the coumarin-modified organosilicon polyurethane main body in a reversible covalent bond mode through photodimerization, so that the biscoumarin end-group polydimethylsiloxane lubricating liquid is combined in the reversible covalent bond mode, and the loss of the lubricating liquid under seawater flushing is effectively reduced.
And meanwhile, the antifouling performance of the coating can be adjusted based on the light response on the surface of the coating, so that the antifouling performance of the super-lubricating coating is enhanced as required. The sunlight contains ultraviolet rays with 254nm UV, and the sunlight can continuously destroy the reversible covalent bond on the surface of the coating through the 254nm UV action, so that the mobility of the biscoumarin-terminated polydimethylsiloxane lubricating liquid is continuously enhanced, the lubricating property and the physical barrier function are enhanced, and the antifouling property is enhanced, so that the phenomenon that more vigorous marine fouling organisms in the daytime adhere and grow on the surface is prevented; under the condition of no illumination, the photo-polymerization action can not occur, and the mobility of the coumarin-terminated polydimethylsiloxane lubricating liquid is not continuously enhanced. Because the growth of fouling organisms at night is slowed down, the low antifouling requirement at night is satisfied. Although sunlight contains 254nm UV and 365nm UV, the photon energy of 254nm UV is higher, and the dimer of coumarin has butane ring, so that the photon is in an unstable state with higher potential energy, the photon of 254nm UV with higher energy is easier to receive, and the photon is destroyed from the dimerization state with higher potential energy to be converted into the non-dimerization state with lower energy, so that the photon is popular in the appearance of "money is difficult to collect and flower Qian Yi". In the preparation process of the coating, pure 365nm ultraviolet light treatment is used in advance, so that coumarin groups of the end groups of the biscoumarin-terminated polydimethylsiloxane lubricating liquid are dimerized and connected with coumarin groups in the coumarin-modified organosilicon polyurethane main body through photodimerization, and are combined in a reversible covalent bond mode; under the combined action of 365nm and 254nm UV in sunlight in the use process, the damage of 254nm UV to dimer is dominant for the reasons, so that the photodimerization reversible bond of coumarin on the surface can be broken, the mobility of coumarin end group polydimethylsiloxane lubricating liquid on the surface is increased, and the lubricating performance and antifouling performance are enhanced.
According to the invention, the activity of the biscoumarin end-group polydimethylsiloxane lubricating liquid on the surface of the coumarin-modified organosilicon polyurethane main body is regulated and controlled by utilizing the photoresponse reversible dimerization behavior of the coumarin compound, so that the loss of the lubricating liquid is reduced, the photoresponsivity of the coating can be used for regulating the antifouling performance as required, the antifouling efficiency is effectively improved, and the service life is prolonged.
Compared with the prior art, the invention has the beneficial effects that:
1. under 365nm ultraviolet treatment in the preparation process of the prepared anti-fouling coating, coumarin groups of the end groups of the biscoumarin end-group polydimethylsiloxane lubricating liquid are connected with coumarin in the coumarin modified organosilicon polyurethane main body in a reversible covalent bond mode through photodimerization, so that the problems that lubricating liquid is easy to run off and the service life is short in the super-lubricating coating injected by the traditional lubricating liquid are effectively reduced due to the fact that the lubricating liquid is combined in the reversible covalent bond mode.
2. According to the invention, the activity of the end group of the biscoumarin end group polydimethylsiloxane lubricating liquid on the surface of the coumarin modified organosilicon polyurethane main body is regulated and controlled by utilizing the photoresponse reversible dimerization behavior of the coumarin compound, so that the surface lubricating property is regulated, the coating can regulate the antifouling strength according to different fouling strengths in daytime and nighttime, the photoresponse is as required, the antifouling efficiency is effectively improved, and the service life is prolonged.
Drawings
FIG. 1 is a mechanism of coumarin-based photoresponsive long-acting superlubricating antifouling paint;
Detailed Description
The invention will be described in further detail with reference to specific examples and comparative examples. The examples will allow a person skilled in the art to more fully understand the invention and are not intended to limit it in any way.
Example 1
The preparation and use methods of the coumarin-based light response long-acting super-lubricating antifouling paint are as follows:
(1) 1 part by weight of 4-methylumbelliferone, 10 parts by weight of epichlorohydrin, 0.1 part by weight of potassium hydroxide and 10 parts by weight of methanol were taken and mixed, and the reaction was stirred at 50℃for 1 hour. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the epoxy coumarin compound.
(2) 1 part by weight of the epoxycoumarin compound prepared in the step (1), 10 parts by weight of the bisaminopropyl end group reactive polydimethylsiloxane (molecular weight 1000) and 10 parts by weight of tetrahydrofuran are mixed, and the reaction is stirred at 50 ℃ for 1 hour. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the biscoumarin end group polydimethylsiloxane lubricating liquid.
(3) 10 parts by weight of dihydroxypropyl end group reactive polydimethylsiloxane (molecular weight 1000), 1 part by weight of diphenylmethane diisocyanate, 1 part by weight of tetrahydrofuran, 1 part by weight of 4, 7-dihydroxycoumarin and 1 part by weight of glycerol are mixed, and the mixture is heated for 1 hour in a nitrogen atmosphere at 60 ℃ to form coumarin modified organic silicon polyurethane feed liquid.
(4) And (3) continuously adding 1 part by weight of the prepared biscoumarin end group polydimethylsiloxane lubricating liquid in the step (2) into the coumarin modified organosilicon polyurethane material in the step (3), and after dispersing and uniformly mixing, radiating with 365nm ultraviolet light and stirring for 1h to obtain the coumarin-based light response long-acting super-lubricating antifouling paint.
(5) The using method of the light response long-acting super-lubricating antifouling paint based on coumarin comprises the following steps: uniformly coating the antifouling paint on the surface to be sprayed in an air spraying mode, wherein the coating thickness of a wet film is 100 mu m; drying under the condition of room temperature of ventilation drying to obtain a dry coating film.
Example 2
The preparation and use methods of the coumarin-based light response long-acting super-lubricating antifouling paint are as follows:
(1) 25 parts by weight of 4-hydroxycoumarin, 250 parts by weight of epichlorohydrin, 2.5 parts by weight of potassium hydroxide and 250 parts by weight of water were mixed, and the reaction was stirred at 65℃for 2 hours. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the epoxy coumarin compound.
(2) 25 parts by weight of the epoxycoumarin compound prepared in (1), 250 parts by weight of the bisaminopropyl end group-reactive polydimethylsiloxane (molecular weight 2500) and 250 parts by weight of ethyl acetate were mixed, and the reaction was stirred at 65℃for 2 hours. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the biscoumarin end group polydimethylsiloxane lubricating liquid.
(3) 250 parts by weight of dihydroxypropyl end group reactive polydimethylsiloxane (molecular weight 2500), 25 parts by weight of triphenylmethane triisocyanate, 250 parts by weight of ethyl acetate, 15 parts by weight of 5, 7-dihydroxy-4-methylcoumarin and 15 parts by weight of hexamethylenediamine are mixed, and the mixture is heated for 2 hours in a nitrogen atmosphere at 65 ℃ to form coumarin modified organosilicon polyurethane feed liquid.
(4) And (3) continuously adding 10 parts by weight of the prepared biscoumarin end group polydimethylsiloxane lubricating liquid in the step (2) into the coumarin modified organosilicon polyurethane material in the step (3), and after dispersing and uniformly mixing, radiating with 365nm ultraviolet light and stirring for 2 hours to obtain the coumarin-based light response long-acting super-lubricating antifouling paint.
(5) The using method of the light response long-acting super-lubricating antifouling paint based on coumarin comprises the following steps: uniformly coating the antifouling paint on the surface to be sprayed in an air spraying mode, wherein the coating thickness of a wet film is 250 mu m; drying under the condition of room temperature of ventilation drying to obtain a dry coating film.
Example 3
The preparation and use methods of the coumarin-based light response long-acting super-lubricating antifouling paint are as follows:
(1) 50 parts by weight of 3-hydroxycoumarin, 500 parts by weight of epichlorohydrin, 5 parts by weight of potassium hydroxide and 500 parts by weight of N, N-dimethylformamide were taken and mixed, and the reaction was stirred at 75℃for 5 hours. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the epoxy coumarin compound.
(2) 50 parts by weight of the epoxycoumarin compound prepared in (1), 500 parts by weight of the bisaminopropyl end group reactive polydimethylsiloxane (molecular weight 5000) and 500 parts by weight of N, N-dimethylformamide were mixed, and the reaction was stirred at 75 ℃ for 2 hours. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the biscoumarin end group polydimethylsiloxane lubricating liquid.
(3) 500 parts by weight of double epoxy group end group reactive polydimethylsiloxane (molecular weight 5000), 50 parts by weight of isophorone diisocyanate, 500 parts by weight of N, N-dimethylformamide, 25 parts by weight of 6, 7-dihydroxycoumarin and 25 parts by weight of triethylamine are mixed, and the mixture is heated for 2 hours under the condition of nitrogen atmosphere and 70 ℃ to form coumarin modified organosilicon polyurethane feed liquid.
(4) And (3) continuously adding 15 parts by weight of the prepared biscoumarin end group polydimethylsiloxane lubricating liquid in the step (2) into the coumarin modified organosilicon polyurethane material in the step (3), and after dispersing and uniformly mixing, radiating with 365nm ultraviolet light and stirring for 2 hours to obtain the coumarin-based light response long-acting super-lubricating antifouling paint.
(5) The using method of the light response long-acting super-lubricating antifouling paint based on coumarin comprises the following steps: uniformly coating the antifouling paint on the surface to be sprayed in an air spraying mode, wherein the coating thickness of a wet film is 500 mu m; drying under the condition of room temperature of ventilation drying to obtain a dry coating film.
Example 4
The preparation and use methods of the coumarin-based light response long-acting super-lubricating antifouling paint are as follows:
(1) 75 parts by weight of 6-hydroxycoumarin, 750 parts by weight of epichlorohydrin, 7.5 parts by weight of potassium hydroxide and 750 parts by weight of ethanol are taken and mixed, and the reaction is stirred at 75 ℃ for 7 hours. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the epoxy coumarin compound.
(2) 75 parts by weight of the epoxycoumarin compound prepared in (1), 750 parts by weight of the bisaminopropyl end group-reactive polydimethylsiloxane (molecular weight 7500) and 750 parts by weight of butyl acetate were mixed, and the reaction was stirred at 75℃for 4 hours. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the biscoumarin end group polydimethylsiloxane lubricating liquid.
(3) 750 parts by weight of double amino propyl end group reactive polydimethylsiloxane (molecular weight 7500), 75 parts by weight of hexamethylene diisocyanate, 750 parts by weight of butyl acetate, 40 parts by weight of 7, 8-dihydroxy-4-methylcoumarin and 40 parts by weight of triethylamine are mixed, and the mixture is heated for 3 hours under the condition of nitrogen atmosphere and 75 ℃ to form coumarin modified organosilicon polyurethane feed liquid.
(4) And (3) continuously adding 25 parts by weight of the prepared biscoumarin end group polydimethylsiloxane lubricating liquid in the step (2) into the coumarin modified organosilicon polyurethane material in the step (3), and after dispersing and uniformly mixing, radiating with 365nm ultraviolet light and stirring for 3 hours to obtain the coumarin-based light response long-acting super-lubricating antifouling paint.
(5) The using method of the light response long-acting super-lubricating antifouling paint based on coumarin comprises the following steps: uniformly coating the antifouling paint on the surface to be sprayed in an air spraying mode, wherein the coating thickness of a wet film is 750 mu m; drying under the condition of room temperature of ventilation drying to obtain a dry coating film.
Example 5
The preparation and use methods of the coumarin-based light response long-acting super-lubricating antifouling paint are as follows:
(1) 100 parts by weight of 5-methylumbelliferone, 1000 parts by weight of epichlorohydrin, 10 parts by weight of potassium hydroxide and 1000 parts by weight of ethanol are taken and mixed, and the reaction is stirred at 100 ℃ for 10 hours. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the epoxy coumarin compound.
(2) 100 parts by weight of the epoxycoumarin compound prepared in the step (1), 1000 parts by weight of the diaminopropyl end group reactive polydimethylsiloxane (molecular weight 10000) and 1000 parts by weight of xylene are taken and mixed, and the reaction is stirred for 5 hours at 100 ℃. And after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the biscoumarin end group polydimethylsiloxane lubricating liquid.
(3) 1000 parts by weight of double amino propyl end group reactive polydimethylsiloxane (molecular weight 10000), 100 parts by weight of hexamethylene diisocyanate, 1000 parts by weight of xylene, 50 parts by weight of 5, 7-dihydroxycoumarin and 50 parts by weight of butanediol are mixed, and the mixture is heated for 4 hours in a nitrogen atmosphere at 80 ℃ to form coumarin modified organic silicon polyurethane feed liquid.
(4) And (3) continuously adding 30 parts by weight of the prepared biscoumarin end group polydimethylsiloxane lubricating liquid in the step (2) into the coumarin modified organosilicon polyurethane material in the step (3), and after dispersing and uniformly mixing, radiating with 365nm ultraviolet light and stirring for 4 hours to obtain the coumarin-based light response long-acting super-lubricating antifouling paint.
(5) The using method of the light response long-acting super-lubricating antifouling paint based on coumarin comprises the following steps: uniformly coating the antifouling paint on the surface to be sprayed in an air spraying mode, wherein the coating thickness of a wet film is 1000 mu m; drying under the condition of room temperature of ventilation drying to obtain a dry coating film.
Performance evaluation results:
(1) Antifouling property of sea
The test method is carried out by referring to national standard GB/T5370-2007 "antifouling paint sample plate shallow sea soaking test method". The base material is a low-carbon steel plate with the thickness of 3mm and the size of 350mm multiplied by 250mm, the shallow sea soaking period is 3 months (8 months-11 months), and the soaking depth is 0.5m.
Stage I: the adhesion of extremely thin mucus was confirmed, but the adhesion of animal species was not confirmed
Stage II: the adhesion of mucus was confirmed, but the adhesion of animal species was not confirmed
III grade: the adhesion of thick mucus was confirmed, but the adhesion of animal species was not confirmed
Grade IV: confirmation of fouling of animal species
V level: the whole of the coating film confirmed the adhesion of animal species.
The results of the actual marine antifouling property test are shown in Table 1.
(2) Long-acting real sea antifouling test
The test method is carried out by referring to national standard GB/T5370-2007 "antifouling paint sample plate shallow sea soaking test method". The base material used was a low carbon steel plate 3mm thick and 350mm x 250mm in size, the immersion depth was 0.5m, and when the area covered by marine organisms was 10% of the area of the template, the shallow sea immersion time at this time was recorded and recorded as the life of the coating.
(3) Photoresponsive properties of surface lubricity:
the surface lubrication performance was characterized by testing the speed of a water droplet (50 μl) sliding on a coating of a certain inclination angle (30 °) and a certain length (72 mm). A video of the drop sliding off the sloped coating surface was taken with a digital camera. The sliding time of the droplet from the start point to the bottom of the ramp was tested by a timer and video editing software. Since the length of the ramp path is known, the sliding velocity of the droplet can be calculated. The average was taken as the drop slip speed to characterize the photoresponsive properties of the surface lubricity.
TABLE 1 test results of antifouling coatings of coumarin-based light responsive long acting superlubricating antifouling coatings
While the invention has been described in detail and with reference to specific embodiments thereof, by way of example only, various modifications and alternatives thereto are contemplated. It should be understood that the invention is not intended to be limited to the particular forms disclosed. The intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the coumarin-based light response long-acting super-lubricating antifouling paint is characterized by comprising the following steps of:
(1) Mixing 1-100 parts by weight of monohydroxy coumarin compound, 10-1000 parts by weight of epichlorohydrin, 0.1-10 parts by weight of potassium hydroxide and 10-1000 parts by weight of solvent alpha, and stirring at 50-100 ℃ for 1-10 hours; after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the epoxy coumarin compound;
(2) Mixing 1-100 parts by weight of epoxy coumarin compound prepared in the step (1), 10-1000 parts by weight of double aminopropyl end group reactive polydimethylsiloxane and 10-1000 parts by weight of solvent beta, and stirring at 50-100 ℃ for 1-5 hours; after removing the solvent by rotary evaporation, washing with water and dichloromethane simultaneously, separating liquid, collecting an organic layer, and drying to obtain the biscoumarin end group polydimethylsiloxane lubricating liquid;
(3) Mixing 10-1000 parts by weight of double-end-group reactive polydimethylsiloxane, 1-100 parts by weight of polyisocyanate, 10-1000 parts by weight of solvent beta, 1-50 parts by weight of dihydroxycoumarin compound and 1-50 parts by weight of polyol or polyamine, and heating for 1-4 hours in a nitrogen atmosphere at 60-80 ℃ to form coumarin modified organic silicon polyurethane feed liquid;
(4) And continuously adding 1-30 parts by weight of biscoumarin end group polydimethylsiloxane lubricating liquid into the coumarin modified organosilicon polyurethane liquid, dispersing and uniformly mixing, and then radiating with 365nm ultraviolet light and stirring for 1-4 hours to obtain the coumarin-based light response long-acting super-lubrication anti-fouling paint.
2. The preparation method of the coumarin-based light response long-acting super-lubricating antifouling paint is characterized in that the monohydroxy coumarin compound is as follows: a composition of one or more of 4-methylumbelliferone, 5-methylumbelliferone, 3-hydroxycoumarin, 4-hydroxycoumarin, 6-hydroxycoumarin and 7-hydroxycoumarin.
3. The method for preparing the coumarin-based light response long-acting super-lubricating antifouling paint according to claim 1, wherein the weight average molecular weight of the double aminopropyl end group reactive polydimethylsiloxane is 1000-10000.
4. The method for preparing the coumarin-based light response long-acting super-lubricating antifouling paint according to claim 1, wherein the weight average molecular weight of the double-end-group reactive polydimethylsiloxane is 1000-10000; the double end group in the formula refers to: one or more of hydroxypropyl, aminopropyl, and epoxy groups.
5. The preparation method of the coumarin-based light response long-acting super-lubricating antifouling paint is characterized in that the polyisocyanate is diisocyanate or triisocyanate, and specifically comprises the following steps: one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and triphenylmethane triisocyanate.
6. The method for preparing the coumarin-based light response long-acting super-lubricating antifouling paint according to claim 1, wherein the dihydroxycoumarin compound is: a composition of one or more of 4, 7-dihydroxycoumarin, 5, 7-dihydroxycoumarin, 6, 7-dihydroxycoumarin, 5, 7-dihydroxy-4-methylcoumarin, 7, 8-dihydroxy-4-methylcoumarin, 7-dihydroxypropyl-4-methylcoumarin, and 7-dihydroxybutyl-4-methylcoumarin.
7. The method for preparing the coumarin-based light response long-acting super-lubricating antifouling paint according to claim 1, wherein the polyol or polyamine is: one or more of glycerol, butanediol, triethylamine and hexamethylenediamine.
8. The preparation method of the coumarin-based light response long-acting super-lubricating antifouling paint is characterized in that the solvent alpha is as follows: one or more of water, methanol, ethanol, N-dimethylformamide.
9. The preparation method of the coumarin-based light response long-acting super-lubricating antifouling paint is characterized in that the solvent beta is as follows: one or more of tetrahydrofuran, xylene, N-dimethylformamide, ethyl acetate and butyl acetate.
10. The method for using the coumarin-based light response long-acting super-lubricating anti-fouling paint is characterized in that the anti-fouling paint obtained by the preparation method according to any one of claims 1-9 is uniformly coated on the surface to be sprayed in an air spraying mode, and the coating thickness of a wet film is 100-1000 mu m; drying under the condition of room temperature of ventilation drying to obtain a dry coating film.
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