阅读说明：本技术 一种透气防腐蚀的涂料及其制备方法 (Breathable anti-corrosion coating and preparation method thereof ) 是由 刘云 于 2021-07-24 设计创作，主要内容包括：本发明公开了一种透气防腐蚀的涂料及其制备方法。本发明首先用丙烯酸六氟丁酯与蚕丝纤维通过含氟侧链发生接枝反应,然后将类弹性蛋白和接枝蚕丝纤维混合后制得蚕丝蛋白混合物,用多巴胺对蚕丝蛋白混合物进行改性后,在改性蚕丝蛋白混合物中的氨基上引入甲基丙烯酸酐合成单官能度的可光引发的多巴胺衍生物后,再与环氧树脂进行混合,同时加入纳米二氧化钛石墨烯后制得透气防腐蚀的涂料。本发明制备的透气防腐蚀的涂料具有抑制污染、粘附性、耐磨性、抗渗透性和色彩多样性的效果。(The invention discloses a breathable anticorrosive coating and a preparation method thereof. According to the invention, hexafluorobutyl acrylate and silk fiber are subjected to a grafting reaction through a fluorine-containing side chain, then elastin-like protein and the grafted silk fiber are mixed to prepare a silk protein mixture, the silk protein mixture is modified by dopamine, methacrylic anhydride is introduced to an amino group in the modified silk protein mixture to synthesize a monofunctional photoinitiable dopamine derivative, and then the modified silk protein mixture is mixed with epoxy resin, and simultaneously nano titanium dioxide graphene is added to prepare the breathable anticorrosive coating. The breathable anticorrosive coating prepared by the invention has the effects of inhibiting pollution, adhesion, wear resistance, permeability resistance and color diversity.)

1. The breathable anticorrosive paint is characterized by mainly comprising, by weight, 30-40 parts of a modified fibroin mixture, 50-60 parts of epoxy resin, 20-30 parts of nano titanium dioxide graphene and 5-10 parts of an auxiliary agent.

2. The coating of claim 1, wherein the modified fibroin mixture comprises a fibroin mixture, dopamine, methacrylic anhydride.

3. The coating of claim 2, wherein the fibroin mixture is prepared by mixing silk fibroin and grafted silk fiber.

4. The coating of claim 3, wherein the grafted silk fiber is prepared by graft reaction of hexafluorobutyl acrylate and silk fiber through fluorine-containing side chain.

5. The breathable anti-corrosion coating according to claim 4, wherein the auxiliary agent is one of chlordane anhydride and antimony trioxide in a flame retardant.

6. The preparation method of the breathable anti-corrosion coating is characterized by mainly comprising the following preparation steps of:

(1) preparing grafted silk fiber: carrying out grafting reaction on hexafluorobutyl acrylate and silk fibers through fluorine-containing side chains to prepare grafted silk fibers;

(2) preparation of fibroin mixture: silk fibroin and grafted silk fiber are mixed to prepare a silk protein mixture;

(3) preparation of modified fibroin mixture: modifying the fibroin mixture by dopamine, and introducing methacrylic anhydride to amino groups in the modified fibroin mixture to synthesize a monofunctional photoinitiable dopamine derivative to prepare a modified fibroin mixture;

(4) preparing the breathable anticorrosive coating: the modified fibroin mixture, the epoxy resin, the nano titanium dioxide graphene and the flame retardant are mixed and reacted to obtain the modified fibroin nano graphene flame retardant.

7. The method for preparing the coating with air permeability and corrosion protection according to claim 6, wherein the method for preparing the grafted silk fiber in the step (1) comprises the following steps: preparing an emulsifier from 12% of ethoxy nonionic fluorocarbon surfactant, 8% of hydroxyalkyl fluorocarbon surfactant and 30% of sorbitan monooleate polyoxyethylene ether according to the mass ratio of 2:1: 5-2: 1:10, stirring at a high speed of 8000-9000 r/min for 1min on a high-speed emulsifying machine, increasing the speed to 11000-12000 r/min, dropwise adding into hexafluorobutyl acrylate under the high-speed emulsifying condition for 3-5 min, and emulsifying for 30min to prepare a finishing liquid for later use; weighing 30-40 parts of silk according to parts by weight, adding the silk into the finishing liquid at a bath ratio of 1:50, heating an emulsifier to 90-100 ℃ under continuous stirring, adding potassium persulfate which is 0.1-0.3 time of the mass of the silk, stirring for 30-40 min, washing with water after the reaction is finished, drying in a drying oven at 70-80 ℃, extracting the dried substance in a Soxhlet extractor for 4-5 h by using an acetone solution with the mass fraction of 25%, then drying, balancing for 20-24 h, and obtaining the grafted silk fiber.

8. The method for preparing the coating with air permeability and corrosion protection according to claim 6, wherein the fibroin mixture prepared in the step (2) is prepared by: mixing silkworm silk fibroin fibers and a lithium bromide solution with the mass fraction of 9.3% according to the mass ratio of 1: 4-1: 5, sealing the mixture with tinfoil paper, putting the mixture into an oven with the temperature of 60-70 ℃ for dissolving for 4-5 hours, taking out the mixture and putting the mixture into a dialysis bag, dialyzing the mixture in deionized water for 36-40 hours, changing water for 5-7 times in the dialysis process, centrifuging the dialyzed solution in a centrifuge with the temperature of 4-5 ℃ at the speed of 8000-9000 rpm for 2-3 times, 15-20 min each time, obtaining a silk fibroin solution after the reaction is finished, immersing the grafted silk fibers in a silk fibroin solution with the concentration of 1% which is 2-3 times of the mass of the grafted silk fibers, carrying out vacuum dry thermal crosslinking for 48-50 hours at the temperature of 60-70 ℃, cooling to 20-25 ℃ in a vacuum state, and taking out the temperature reduction to obtain a silk fibroin mixture.

9. The method for preparing the coating with air permeability and corrosion protection according to claim 6, wherein the modified fibroin mixture prepared in the step (3) is prepared by: preparing 2-3 g/L of dopamine acid solution, adjusting the pH value of the dopamine acid solution to 8 by using trihydroxymethyl aminomethane and trihydroxymethyl aminomethane hydrochloride at a bath ratio of 1:80, adding methacrylic anhydride with the mass of 0.2-0.3 times of that of the dopamine acid solution, stirring and mixing for 20-30 min, soaking the fibroin mixture in the dopamine acid solution, carrying out constant-temperature continuous oscillation treatment at 45-50 ℃ for 20-24 h in a low-noise oscillation type sample dyeing machine, taking out a product, washing with water, and drying at 60-70 ℃ to obtain the modified fibroin mixture.

10. The method for preparing a coating with gas-permeable anticorrosion according to claim 6, wherein the method for preparing the coating with gas-permeable anticorrosion in the step (4) comprises: the modified fibroin mixture and epoxy resin are mixed and stirred uniformly according to the mass ratio of 1: 3-3: 5, after ultrasonic dispersion is carried out for 20-30 min, then nano titanium dioxide graphene with the mass of 0.2-0.3 times that of the epoxy resin is added, the mixture is continuously stirred and uniformly heated to 90-100 ℃, after ultrasonic dispersion is carried out for 1-1.5 h, the mixture is dispersed at a high speed of 800-900 r/min for 30-40 min by using a stirrer, and after the reaction is finished, a flame retardant antimony trioxide is added, stirred, dissolved and mixed, so that the breathable anticorrosive coating is prepared.

Technical Field

The invention relates to the technical field of new materials, in particular to a breathable anticorrosive coating and a preparation method thereof.

Background

Along with the development of society and the requirements of low carbon and environmental protection, energy conservation and consumption reduction become important problems in energy application and scientific research, various functional coatings are developed under the social background, great progress is made in the expansion of various application fields, and the requirements of people on the coatings are higher and higher.

Disclosure of Invention

The invention aims to provide a breathable anti-corrosion coating and a preparation method thereof, which aim to solve the problems in the prior art.

In order to solve the technical problems, the invention provides the following technical scheme: a breathable anti-corrosion coating mainly comprises the following components in parts by weight:

30-40 parts of modified fibroin mixture, 50-60 parts of epoxy resin, 20-30 parts of nano titanium dioxide graphene and 5-10 parts of auxiliary agent.

Further, the modified fibroin mixture comprises fibroin mixture, dopamine and methacrylic anhydride.

Furthermore, the fibroin mixture is prepared by mixing elastin-like protein and grafted silk fiber.

Furthermore, the grafted silk fiber is prepared by carrying out grafting reaction on hexafluorobutyl acrylate and silk fiber through a fluorine-containing side chain.

Further, the auxiliary agent is one of chlordane anhydride and antimony trioxide in the flame retardant.

Further, the preparation method of the breathable anti-corrosion coating is characterized by mainly comprising the following preparation steps:

(1) preparing grafted silk fiber: carrying out grafting reaction on hexafluorobutyl acrylate and silk fibers through fluorine-containing side chains to prepare grafted silk fibers;

(2) preparation of fibroin mixture: mixing the elastin-like protein and the grafted silk fiber to obtain a silk protein mixture;

(3) preparation of modified fibroin mixture: modifying the fibroin mixture by dopamine, and introducing methacrylic anhydride to amino groups in the modified fibroin mixture to synthesize a monofunctional photoinitiable dopamine derivative to prepare a modified fibroin mixture;

(4) preparing the breathable anticorrosive coating: the modified fibroin mixture, the epoxy resin, the nano titanium dioxide graphene and the flame retardant are mixed and reacted to obtain the modified fibroin nano graphene flame retardant.

Further, the preparation method of the grafted silk fiber in the step (1) comprises the following steps: preparing an emulsifier from 12% of ethoxy nonionic fluorocarbon surfactant, 8% of hydroxyalkyl fluorocarbon surfactant and 30% of sorbitan monooleate polyoxyethylene ether according to the mass ratio of 2:1: 5-2: 1:10, stirring at a high speed of 8000-9000 r/min for 1min on a high-speed emulsifying machine, increasing the speed to 11000-12000 r/min, dropwise adding into hexafluorobutyl acrylate under the high-speed emulsifying condition for 3-5 min, and emulsifying for 30min to prepare a finishing liquid for later use; weighing 30-40 parts of silk according to parts by weight, adding the silk into the finishing liquid at a bath ratio of 1:50, heating an emulsifier to 90-100 ℃ under continuous stirring, adding potassium persulfate which is 0.1-0.3 time of the mass of the silk, stirring for 30-40 min, washing with water after the reaction is finished, drying in a drying oven at 70-80 ℃, extracting the dried substance in a Soxhlet extractor for 4-5 h by using an acetone solution with the mass fraction of 25%, then drying, balancing for 20-24 h, and obtaining the grafted silk fiber.

Further, the preparation method of the fibroin mixture in the step (2) comprises the following steps: mixing silkworm silk fibroin fibers and a lithium bromide solution with the mass fraction of 9.3% according to the mass ratio of 1: 4-1: 5, sealing the mixture with tinfoil paper, putting the mixture into an oven with the temperature of 60-70 ℃ for dissolving for 4-5 hours, taking out the mixture and putting the mixture into a dialysis bag, dialyzing the mixture in deionized water for 36-40 hours, changing water for 5-7 times in the dialysis process, centrifuging the dialyzed solution in a centrifuge with the temperature of 4-5 ℃ at the speed of 8000-9000 rpm for 2-3 times, 15-20 min each time, obtaining a silk fibroin solution after the reaction is finished, immersing the grafted silk fibers in a silk fibroin solution with the concentration of 1% which is 2-3 times of the mass of the grafted silk fibers, carrying out vacuum dry thermal crosslinking for 48-50 hours at the temperature of 60-70 ℃, cooling to 20-25 ℃ in a vacuum state, and taking out the temperature reduction to obtain a silk fibroin mixture.

Further, the preparation method of the modified fibroin mixture in the step (3) comprises the following steps: preparing 2-3 g/L of dopamine acid solution, adjusting the pH value of the dopamine acid solution to 8 by using trihydroxymethyl aminomethane and trihydroxymethyl aminomethane hydrochloride at a bath ratio of 1:80, adding methacrylic anhydride with the mass of 0.2-0.3 times of that of the dopamine acid solution, stirring and mixing for 20-30 min, soaking the fibroin mixture in the dopamine acid solution, carrying out constant-temperature continuous oscillation treatment at 45-50 ℃ for 20-24 h in a low-noise oscillation type sample dyeing machine, taking out a product, washing with water, and drying at 60-70 ℃ to obtain the modified fibroin mixture.

Further, the preparation method of the breathable anti-corrosion coating in the step (4) comprises the following steps: the modified fibroin mixture and epoxy resin are mixed and stirred uniformly according to the mass ratio of 1: 3-3: 5, after ultrasonic dispersion is carried out for 20-30 min, then nano titanium dioxide graphene with the mass of 0.2-0.3 times that of the epoxy resin is added, the mixture is continuously stirred and uniformly heated to 90-100 ℃, after ultrasonic dispersion is carried out for 1-1.5 h, the mixture is dispersed at a high speed of 800-900 r/min for 30-40 min by using a stirrer, and after the reaction is finished, a flame retardant antimony trioxide is added, stirred, dissolved and mixed, so that the breathable anticorrosive coating is prepared.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, hexafluorobutyl acrylate and silk fiber are subjected to a grafting reaction through a fluorine-containing side chain, then elastin-like protein and the grafted silk fiber are mixed to prepare a silk protein mixture, the silk protein mixture is modified by dopamine, methacrylic anhydride is introduced to an amino group in the modified silk protein mixture to synthesize a monofunctional photoinitiable dopamine derivative, and then the modified silk protein mixture is mixed with epoxy resin, and simultaneously nano titanium dioxide graphene is added to prepare the breathable anticorrosive coating.

The hexafluorobutyl acrylate enables the surface of silk fiber to be rough, high molecular polymer is attached to the silk fiber, the longitudinal section of the silk fiber becomes rough, the plumpness is good, and after the hexafluorobutyl acrylate is combined with the fabric, fluorine atoms form a negative electricity protection layer on the fabric, so that the surface tension of the fabric is obviously reduced, the surface contact angle is obviously increased, external pollutants are difficult to enter, and a good pollution inhibiting effect is achieved.

The dopamine can be oxidized and self-polymerized on the surface of the fibroin mixture, amino and phenolic hydroxyl functional groups are introduced, the temperature is increased to promote the dopamine to perform self-polymerization reaction on the fibroin mixture, and the reaction between carboxyl and amino groups on the fibroin mixture and phenolic hydroxyl groups in polydopamine molecules is promoted, so that the amount of polydopamine deposited on the fibroin mixture is increased, a large amount of polydopamine can absorb external heat and refract out sun seven-color light through illumination to cause the color change of a coating, and when the coating is applied to a fabric, the color of the fabric can be changed along with the change of the temperature, so that the fabric has the colorfulness and novelty; and the dopamine modified fibroin mixture can form a three-dimensional structure support in epoxy resin, and the photoinitiator dopamine derivative with single functionality synthesized by methacrylic anhydride can coat the cross points between the epoxy resin and the silk fiber to stabilize the three-dimensional structure support, improve the stability of the coating, and form a porous film between the silk and the silk.

The charge transfer exists between the nano titanium dioxide graphene added into the epoxy resin, so that a large amount of charges are accumulated on the surface of the epoxy resin, the surface of the coating is in flashover, methacrylic anhydride is introduced to an amino group in the modified silk protein mixture to synthesize a monofunctional photoinitiated dopamine derivative which can act together with the grafted silk fiber to perform fluorination treatment on the surface layer of the epoxy resin, a shielding layer is formed on the surface layer of the epoxy resin to weaken a local electric field, inhibit the injection of the charges, accelerate the dissipation speed of the charges on the surface of the epoxy resin and improve the insulativity of the coating, meanwhile, the methacrylic anhydride can be intertwined with the grafted silk fiber, so that the molecular chains of the methacrylic anhydride and the grafted silk fiber are linked more tightly, the three-dimensional network structure of the silk protein mixture in the epoxy resin is enhanced, the wear resistance of the acrylic anhydride is improved, and the surface appearance of the epoxy resin is in a sheet structure, the nano titanium dioxide graphene and the dopamine derivative are polymerized through the structure, so that the agglomeration in the epoxy resin is reduced, the nano titanium dioxide graphene and the dopamine derivative are uniformly dispersed in the epoxy resin, the compatibility of the coating and the fabric is improved, gaps formed by etching of external harmful substances can be effectively repaired, and the impermeability of the coating is enhanced.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

To more clearly illustrate the method of the present invention, the following examples are given, and the method of testing each index of the air-permeable anticorrosive coating prepared in the following examples is as follows:

corrosion resistance: the corrosion resistance test is carried out on the breathable anti-corrosion coating prepared by the components of example 1, example 2 and comparative example 1; electrochemical test by using a CHI920D scanning electrochemical microscope workstation, a three-electrode system, a platinum electrode as an auxiliary electrode, a saturated calomel electrode as a reference electrode, a 1cm x 1cm galvanized iron test piece as a working electrode, and a sodium chloride solution with the mass fraction of 3.5%, the corrosion potential and the corrosion potential E of the breathable anti-corrosion coating prepared by the components of example 1, example 2 and comparative example 1 after being soaked in the 3.5% sodium chloride solution for 15min are measured_coorThe more positive, the higher the corrosion resistance.

Insulating property: the air-permeable anticorrosive coatings prepared by the components of example 1, example 2 and comparative example 2 were subjected to an insulation test; the testing method is a three-electrode testing method, the polarization time is 100s, the volume resistivity of each component is measured at room temperature, and the larger the volume resistivity is, the better the insulation property is.

Example 1

A breathable anti-corrosion coating mainly comprises the following components in parts by weight: 40 parts of modified fibroin mixture, 60 parts of epoxy resin, 30 parts of nano titanium dioxide graphene and 10 parts of auxiliary agent.

The preparation method of the breathable anti-corrosion coating mainly comprises the following preparation steps:

(1) preparing grafted silk fiber: carrying out grafting reaction on hexafluorobutyl acrylate and silk fibers through fluorine-containing side chains to prepare grafted silk fibers;

(2) preparation of fibroin mixture: mixing the elastin-like protein and the grafted silk fiber to obtain a silk protein mixture;

(3) preparation of modified fibroin mixture: modifying the fibroin mixture by dopamine, and introducing methacrylic anhydride to amino groups in the modified fibroin mixture to synthesize a monofunctional photoinitiable dopamine derivative to prepare a modified fibroin mixture;

(4) preparing the breathable anticorrosive coating: the modified fibroin mixture, the epoxy resin, the nano titanium dioxide graphene and the flame retardant are mixed and reacted to obtain the modified fibroin nano graphene flame retardant.

Further, the preparation method of the grafted silk fiber in the step (1) comprises the following steps: preparing an emulsifier from 12% of ethoxy nonionic fluorocarbon surfactant, 8% of hydroxyalkyl fluorocarbon surfactant and 30% of sorbitan monooleate polyoxyethylene ether according to the mass ratio of 2:1:10, stirring at a high speed of 9000r/min for 1min on a high-speed emulsifying machine, increasing the speed to 12000r/min, controlling the dropping time to be 5min under the high-speed emulsifying condition, dropping into hexafluorobutyl acrylate dropwise, and emulsifying for 30min to prepare a finishing liquid for later use; weighing 40 parts of silk according to the parts by weight, adding the silk into the finishing liquid at a bath ratio of 1:50, heating an emulsifier to 100 ℃ under continuous stirring, adding potassium persulfate which is 0.3 time of the mass of the silk, stirring for 40min, washing with water after the reaction is finished, drying in an oven at 80 ℃, extracting the dried substance in a Soxhlet extractor for 5h by using an acetone solution with the mass fraction of 25%, drying, and balancing for 24h to obtain the grafted silk fiber.

Further, the preparation method of the fibroin mixture in the step (2) comprises the following steps: mixing bombyx mori silk fibroin fibers and a lithium bromide solution with the mass fraction of 9.3% according to the mass ratio of 1:5, sealing the ports with tinfoil paper, putting the ports into an oven with the temperature of 70 ℃ for dissolving for 5 hours, taking out the ports and putting the ports into a dialysis bag, dialyzing the ports in deionized water for 40 hours, changing water for 7 times during the dialysis process, centrifuging the solution after the dialysis in a centrifuge with the temperature of 5 ℃ for 3 times at the speed of 9000rpm for 20 minutes each time, obtaining silk fibroin solution after the reaction is finished, immersing the grafted silk fibers in the silk fibroin solution with the concentration of 1% which is 3 times of the mass of the grafted silk fibers, carrying out vacuum dry thermal crosslinking at the temperature of 70 ℃ for 50 hours, cooling to the temperature of 25 ℃ in a vacuum state, and taking out the grafted silk fibers to obtain the silk protein mixture.

Further, the preparation method of the modified fibroin mixture in the step (3) comprises the following steps: preparing a dopamine acid solution with the concentration of 3g/L, adjusting the pH value of the dopamine acid solution to 8 by using trihydroxymethyl aminomethane and trihydroxymethyl aminomethane hydrochloride with the bath ratio of 1:80, adding methacrylic anhydride with the mass of 0.3 times of that of the dopamine acid solution, stirring and mixing for 30min, soaking the fibroin mixture in the dopamine acid solution, carrying out constant-temperature continuous oscillation treatment at 50 ℃ for 24h in a low-noise oscillation type sample dyeing machine, taking out a product, washing with water, and drying at 70 ℃ to obtain the modified fibroin mixture.

Further, the preparation method of the breathable anti-corrosion coating in the step (4) comprises the following steps: uniformly mixing and stirring the modified fibroin mixture and the epoxy resin according to the mass ratio of 3:5, performing ultrasonic dispersion for 30min, adding nano titanium dioxide graphene with the mass of 0.3 time that of the epoxy resin, continuously stirring uniformly, heating to 100 ℃, performing ultrasonic dispersion for 1.5h, then performing high-speed dispersion for 40min at the speed of 900r/min by using a stirrer, adding antimony trioxide with the mass of 0.2 time that of the epoxy resin after the reaction is finished, stirring, dissolving and mixing to obtain the breathable anticorrosive coating.

Example 2

A breathable anti-corrosion coating mainly comprises the following components in parts by weight: 30 parts of modified fibroin mixture, 50 parts of epoxy resin, 20 parts of nano titanium dioxide graphene and 5 parts of auxiliary agent.

The preparation method of the breathable anti-corrosion coating mainly comprises the following preparation steps:

(1) preparing grafted silk fiber: carrying out grafting reaction on hexafluorobutyl acrylate and silk fibers through fluorine-containing side chains to prepare grafted silk fibers;

(2) preparation of fibroin mixture: mixing the elastin-like protein and the grafted silk fiber to obtain a silk protein mixture;

(3) preparation of modified fibroin mixture: modifying the fibroin mixture by dopamine, and introducing methacrylic anhydride to amino groups in the modified fibroin mixture to synthesize a monofunctional photoinitiable dopamine derivative to prepare a modified fibroin mixture;

(4) preparing the breathable anticorrosive coating: the modified fibroin mixture, the epoxy resin, the nano titanium dioxide graphene and the flame retardant are mixed and reacted to obtain the modified fibroin nano graphene flame retardant.

Further, the preparation method of the grafted silk fiber in the step (1) comprises the following steps: preparing an emulsifier from 12% of ethoxy nonionic fluorocarbon surfactant, 8% of hydroxyalkyl fluorocarbon surfactant and 30% of sorbitan monooleate polyoxyethylene ether according to the mass ratio of 2:1:5, stirring at a high speed of 8000-9000 r/min for 1min on a high-speed emulsifying machine, increasing the speed to 11000r/min, controlling the dropping time to be 3min under the high-speed emulsifying condition, dropping into hexafluorobutyl acrylate dropwise, and emulsifying for 30min to prepare a finishing liquid for later use; weighing 30 parts of silk according to the parts by weight, adding the silk into the finishing liquid at a bath ratio of 1:50, heating an emulsifier to 90 ℃ under continuous stirring, adding potassium persulfate of which the mass is 0.1 time that of the silk, stirring for 30min, washing with water after the reaction is finished, drying in a 70 ℃ oven, extracting the dried substance in a Soxhlet extractor for 4h by using an acetone solution with the mass fraction of 25%, drying, and balancing for 20h to obtain the grafted silk fiber.

Further, the preparation method of the fibroin mixture in the step (2) comprises the following steps: mixing bombyx mori silk fibroin fibers and a lithium bromide solution with the mass fraction of 9.3% according to the mass ratio of 1:4, sealing the ports with tinfoil paper, putting the ports into an oven with the temperature of 60 ℃ for dissolving for 4 hours, taking out the ports and putting the ports into a dialysis bag, dialyzing the ports in deionized water for 36 hours, changing water for 5 times during the dialysis process, centrifuging the solution after the dialysis in a centrifuge with the temperature of 4 ℃ for 2 times at the speed of 8000rpm for 15 minutes each time to obtain a silk fibroin solution after the reaction is finished, immersing the grafted silk fibers in the silk fibroin solution with the concentration of 1% and the mass of 2 times of the grafted silk fibers, carrying out vacuum dry thermal crosslinking at the temperature of 60 ℃ for 48 hours, cooling to the temperature of 20 ℃ in a vacuum state, and taking out the grafted silk fibers to obtain a silk protein mixture.

Further, the preparation method of the modified fibroin mixture in the step (3) comprises the following steps: preparing 2g/L dopamine acid solution, wherein the bath ratio is 1:80, regulating the pH value of the dopamine acid solution to 8 by using trihydroxymethyl aminomethane and trihydroxymethyl aminomethane hydrochloride, adding methacrylic anhydride with the mass of 0.2 times of that of the dopamine acid solution, stirring and mixing for 20min, soaking the fibroin mixture in the dopamine acid solution, carrying out constant-temperature continuous oscillation treatment at 45 ℃ for 20h in a low-noise oscillation type sample dyeing machine, taking out a product, washing with water, and drying at 60 ℃ to obtain the modified fibroin mixture.

Further, the preparation method of the breathable anti-corrosion coating in the step (4) comprises the following steps: uniformly mixing and stirring the modified fibroin mixture and the epoxy resin according to the mass ratio of 1:3, performing ultrasonic dispersion for 20min, adding nano titanium dioxide graphene with the mass of 0.2 time that of the epoxy resin, continuously stirring uniformly, heating to 90 ℃, performing ultrasonic dispersion for 1h, then performing high-speed dispersion for 30min at the speed of 800r/min by using a stirrer, adding antimony trioxide with the mass of 0.1 time that of the epoxy resin after the reaction is finished, stirring, dissolving and mixing to obtain the breathable anticorrosive coating.

Comparative example 1

The formulation of comparative example 1 was the same as example 1. The method for producing the coating material with gas permeation and corrosion prevention is different from that of example 1 only in that the production process of step (1) is not performed, and the rest of the production steps are the same as those of example 1.

Comparative example 2

The formulation of comparative example 1 was the same as example 1. The method for producing the coating material with gas permeation and corrosion prevention is different from that of example 1 only in that the production process of step (3) is not performed, and the rest of the production steps are the same as those of example 1.

Effect example 1

The following table 1 shows the results of the corrosion resistance tests of the breathable anticorrosive coatings obtained in examples 1 and 2 according to the invention and in comparative example 1.

TABLE 1

	Corrosion potential Ecoor
		Example 1	-0.243
Example 2	-0.236
		Comparative example 1	-0.672

The above table shows that the breathable anticorrosive coatings prepared in examples 1 and 2 have good corrosion resistance, and the components in comparative example 1 are poor, which indicates that hexafluorobutyl acrylate makes the surface of silk fiber rough, high molecular polymer adheres to the silk fiber, the longitudinal section of the silk fiber is thick, and the plumpness of the silk fiber is good.

Effect example 2

Table 2 below shows the results of the insulation performance tests of the breathable anticorrosive coatings obtained according to examples 1 and 2 of the invention and comparative example 2.

TABLE 2

	Volume resistivity (omega cm)
		Example 1	6.48×1016
Example 2	6.42×1016
		Comparative example 2	4.42×1016

As can be seen from the above table, the insulating properties of the breathable anticorrosive coatings prepared in examples 1 and 2 are better, while the insulating properties of the breathable anticorrosive coatings prepared in comparative example 2 are not good, which indicates that the incorporation of methacrylic anhydride into the amino group of the modified silk protein mixture to synthesize the monofunctional photoinitiated dopamine derivative can act together with the grafted silk fiber to perform fluorination treatment on the epoxy resin surface layer, so as to form a shielding layer on the epoxy resin surface layer, weaken the local electric field, inhibit the injection of charges, accelerate the dissipation speed of charges on the epoxy resin surface, and improve the insulating properties of the coatings.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.