Organic silicon modified waterproof anticorrosive paint and preparation method thereof

Abstract

The invention relates to the technical field of waterproof anticorrosive coatings, in particular to an organic silicon modified waterproof anticorrosive coating and a preparation method thereof.By introducing organic silicon modified waterborne polyurethane, the coating has excellent waterproof performance, organic silicon has the advantages of being low in surface energy, good in weather resistance and high in chemical stability, moisture permeation can be effectively prevented, and the service life of the coating is prolonged. Meanwhile, the polyurethane component in the organic silicon modified waterborne polyurethane has excellent adhesive force and elasticity, so that the binding force between the coating and a base material can be enhanced, and the waterproof effect is further improved; and secondly, the modified graphene oxide composite material is subjected to composite modification of p-phenylenediamine and polyaniline, so that not only can the dispersity and compatibility of graphene in the coating be improved, but also the mechanical strength, wear resistance and toughness of the coating can be enhanced, and corrosion of a corrosive medium to a base material can be effectively prevented.

Description

Technical Field

[0001] The present invention relates to the technical field of waterproof and anti-corrosion coatings, and in particular to an organosilicon-modified waterproof and anti-corrosion coating and a preparation method thereof. Background Art

[0002] In the current field of building materials and protective coatings, waterproofing and anti-corrosion are two crucial performance indicators. Although traditional coating systems can meet basic waterproofing and anti-corrosion requirements to a certain extent, they often show great limitations when facing complex and changeable natural environments and extreme use conditions. For example, although solvent-based coatings have good permeability and adhesion, the volatile organic compounds they contain not only pollute the environment, but also pose a threat to the health of construction workers. At the same time, these coatings are prone to aging, cracking, and falling off when exposed to harsh environments for a long time, such as high humidity, strong acids and alkalis, and ultraviolet radiation, thereby losing their waterproof and anti-corrosion effects.

[0003] In recent years, with the enhancement of environmental awareness and the advancement of science and technology, water-based paints have gradually become the mainstream trend of the development of the paint industry. Water-based paints use water as a solvent and have the advantages of low volatile organic compound emissions, environmental safety, and easy construction. However, pure water-based paints often cannot meet the needs of high-end applications in terms of waterproof and anti-corrosion performance. Therefore, how to maintain the environmental advantages of water-based paints while improving their waterproof and anti-corrosion performance has become a technical problem that needs to be solved urgently in the current paint industry. Summary of the invention

[0004] In view of the above-mentioned shortcomings of the prior art, the present invention provides a silicone-modified waterproof and anti-corrosion coating and a preparation method thereof, which can effectively solve the problems of poor environmental protection and waterproof and anti-corrosion performance of the coating in the prior art.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions: An organosilicon-modified waterproof and anticorrosive coating, the organosilicon-modified waterproof and anticorrosive coating is composed of the following components: organosilicon-modified waterborne polyurethane, modified graphene oxide composite material, antibacterial nanocomposite material, filler component, silane coupling agent KH-560, dispersant, defoamer, thickener and leveling agent; The organosilicon-modified waterborne polyurethane is prepared by composite-modifying the waterborne polyurethane with epoxy resin and organosilicon; The modified graphene oxide composite material is prepared by compounding p-phenylenediamine-modified graphene oxide and polyaniline; The antibacterial nano composite material is prepared by compounding copper oxide and silver ions.

[0006] Furthermore, the preparation steps of the silicone-modified waterborne polyurethane are: Step 1, add 5-6g of polypropylene glycol, 4-5g of dimethyl silicone oil and 10-12g of isophorone diisocyanate into a flask, mix well, add 0.3-0.4g of dibutyltin dilaurate in a water bath at 70°C, stir and react for 2h, and record the result as a mixed component; Step 2, after cooling the mixed components to 50° C., 1.8-2 g of 1,4-butanediol, 2.2-2.4 g of 2,2-bis(hydroxymethyl)propionic acid and 8-10 g of acetone are added, and after stirring and dispersing, the temperature is raised to 70° C. and kept for reaction for 2 hours. The obtained product is recorded as a silicone-modified waterborne polyurethane prepolymer; Step 3: add 2-3 g of epoxy resin to the organosilicon-modified waterborne polyurethane prepolymer, stir and mix, and react in a water bath at 70° C. for 2 h. Then, add 1-2 g of triethylamine and continue to react for 2 h. Then, add 15-20 g of deionized water and stir vigorously for 30 min. The result is the organosilicon-modified waterborne polyurethane.

[0007] Furthermore, the specific operation of uniform mixing in step 1 is stirring at a stirring speed of 500 r / min for 30 minutes, the stirring speed of the stirring reaction in step 1 is 200 r / min, the specific operation of stirring and dispersing in step 2 is stirring at a stirring speed of 300 r / min for 10 minutes, the specific operation of stirring and mixing in step 3 is stirring at a stirring speed of 200 r / min for 20 minutes, and the stirring speed of the vigorous stirring in step 3 is 600 r / min.

[0008] Furthermore, the preparation steps of the modified graphene oxide composite material are: Step A, pour 0.5-0.7g of graphene oxide and 100mL of deionized water into a flask, add 1-2g of p-phenylenediamine and 1-2mL of ammonia water after ultrasonic treatment, stir and react at a water bath temperature of 90°C for 3h, filter with 0.22μm polytetrafluoroethylene filter paper, wash with anhydrous ethanol and deionized water three times in sequence, place in a freeze dryer and dry to obtain modified graphene oxide; Step B, add 2-3g of modified graphene oxide and 50-55mL of deionized water into a flask, add 1-2g of dodecylbenzenesulfonic acid after mechanical stirring at room temperature for 30min, stir and emulsify at a water bath temperature of 50°C for 30min, add 1-2g of aniline and continue stirring for 10min, the result is recorded as the reaction component; Step C, placing the reaction components in an ice water bath at 0°C, adding a 10% by mass fraction of ammonium persulfate aqueous solution until the color turns blue, then stopping the addition and stirring the reaction for 6 hours, filtering and removing the filtrate, washing with anhydrous ethanol and deionized water three times in sequence, and drying in a freeze dryer to obtain a modified graphene oxide composite material.

[0009] Furthermore, the specific operation of the ultrasonic treatment in step A is ultrasonic dispersion at a frequency of 30 kHz for 30 minutes, the stirring speed of the stirring reaction in step A is 200 r / min, the stirring speed of the mechanical stirring in step B is 500 r / min, the stirring speed of the stirring emulsification in step B is 300 r / min, and the dripping rate in step C is 1 drop / s.

[0010] Furthermore, the preparation steps of the antibacterial nanocomposite material are: Step I, adding 0.8-1 g of natural honey to 50 mL of 10 g / L copper acetate solution under vigorous stirring, continuing stirring at the original stirring speed for 10 min, adding 0.05-0.06 g of silver nitrate and performing ultrasonic treatment, the result is recorded as the reaction system; Step II, place the reaction system in a water bath at 70°C, add 25mL of 10g / L sodium hydroxide solution, continue stirring at the original stirring speed for 1h, and then centrifuge to obtain a precipitated product. Wash the precipitated product three times with anhydrous ethanol and deionized water in sequence, and then dry it to obtain an antibacterial nanocomposite material.

[0011] Furthermore, the stirring speed of the vigorous stirring condition in step I is 800 r / min, the specific operation of the ultrasonic treatment in step I is ultrasonic dispersion at a frequency of 30 kHz for 5 minutes, the specific operation of the centrifugal treatment in step II is centrifugation at a speed of 10000 r / min for 5 minutes, and the specific operation of the drying treatment in step II is drying in a vacuum drying oven at 60°C to constant weight.

[0012] Furthermore, the preparation method of the filler component is: 30-32 parts of water-reducing powder, 25-28 parts of iron oxide red, 30-33 parts of mica powder, 35-36 parts of talc powder, 40-42 parts of zinc phosphate and 50-55 parts of nano titanium dioxide are weighed by weight, poured into a mixer, and stirred and mixed at a stirring speed of 200 r / min to obtain the product.

[0013] A method for preparing an organosilicon-modified waterproof and anticorrosive coating, the preparation method comprising: S1, weighing 4-5 parts by weight of filler component and 1-2 parts by weight of silane coupling agent KH-560 into a ball mill, adding 20-25 parts by weight of anhydrous ethanol, 5-6 parts by weight of modified graphene oxide composite material and 3-4 parts by weight of antibacterial nanocomposite material after ball milling for 10 minutes, stirring and dispersing uniformly, and recording the obtained mixture as filler mixed component; S2. Pour the filler mixture into 60-80 parts by weight of organosilicon-modified waterborne polyurethane, add 2-3 parts by weight of dispersant, 1-2 parts by weight of defoamer, 1-3 parts by weight of thickener and 2-3 parts by weight of leveling agent under stirring, and obtain the organosilicon-modified waterproof and anticorrosive coating after ultrasonic treatment.

[0014] Furthermore, the specific operation of stirring and dispersing uniformly in S1 is stirring at a stirring speed of 500 r / min for 10 min, and the specific operation of ultrasonic treatment in S2 is ultrasonic dispersion at a frequency of 28-30 kHz for 30 min.

[0015] The present invention provides an organosilicon-modified waterproof and anticorrosive coating and a preparation method thereof. Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention introduces organic silicon modified waterborne polyurethane to make the coating have excellent waterproof performance. Organic silicon has the characteristics of low surface energy, good weather resistance and high chemical stability, can effectively prevent water penetration, and improve the waterproof performance of the coating. At the same time, the polyurethane component in the organic silicon modified waterborne polyurethane has excellent adhesion and elasticity, can enhance the bonding force between the coating and the substrate, and further improve the waterproof effect; secondly, the modified graphene oxide composite material can not only improve the dispersibility and compatibility of graphene in the coating, but also enhance the mechanical strength, wear resistance and toughness of the coating, and can effectively prevent the corrosion of the corrosive medium to the substrate.

[0016] 2. The antibacterial nanocomposite material prepared by the composite of copper oxide and silver ions in the present invention has a broad-spectrum antibacterial effect, can effectively inhibit the growth of microorganisms such as bacteria and molds, add an additional biological protection layer to the coating, and prevent the coating from failing due to microbial corrosion by inhibiting the growth of microorganisms such as bacteria; secondly, the present invention adopts water-based polyurethane as the base material, which can avoid the volatilization of harmful solvents in traditional solvent-based coatings and reduce pollution to the environment. At the same time, the filler components in the coating, such as water-reducing powder, iron red, mica powder, etc., are all non-toxic and harmless environmentally friendly materials, which can further improve the environmental performance of the coating. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] The present invention will be further described below in conjunction with the embodiments.

[0019] The sources of some components in the embodiments and comparative examples are as follows: Polypropylene glycol, dimethicone, isophorone diisocyanate, and acetone, analytical grade, Aladdin Company; Dibutyltin dilaurate, chemically pure, from Tianjin Chemical Reagent Factory No. 1; 1,4-Butanediol, analytical grade, from Shanghai Jianxin Chemical Co., Ltd. Reagent Factory; Triethylamine, analytical grade, Tianjin Fuyu Fine Chemical Co., Ltd.; 2,2-Bis(hydroxymethyl)propionic acid, analytical grade, Shantou Xilong Chemical Co., Ltd.; Epoxy resin, industrial grade, Southwest Chemical Industry Co., Ltd., Jiangxi Province; Graphene oxide was prepared by the Hummer method; p-Phenylenediamine, analytical grade, Shanghai MacLean Biochemical Technology Co., Ltd.; Ammonia water, dodecylbenzenesulfonic acid, aniline, ammonium persulfate, Shanghai Guoyao Lushi Chemical Reagent Co., Ltd.; Copper acetate, silver nitrate, and sodium hydroxide were of analytical grade and were purchased from Shanghai Runjie Chemical Reagent Co., Ltd. Natural honey, with an enzyme activity value of 200+, was purchased from Beijing Cishengtang Beekeeping Co., Ltd.; Water-suppressing powder and iron red, analytical grade, from Tianjin Fuchen Chemical Reagent Factory; Mica powder, 800 mesh, Hefei Xionglu Chemical Co., Ltd.; Talc, 1250 mesh, industrial grade, Changzhou Youchang Chemical Co., Ltd.; Zinc phosphate, industrial grade, Shanghai Chemical Reagent Company; Dispersant, industrial grade, Shanghai Buding Chemical; Defoaming agent, industrial grade, Shandong Jinhaichuan Chemical Co., Ltd.; Thickener, leveling agent, industrial grade, Guangzhou Guanzhi Chemical Co., Ltd.; Embodiment 1: An organosilicon-modified waterproof and anticorrosive coating of this embodiment, the organosilicon-modified waterproof and anticorrosive coating is composed of the following components: organosilicon-modified waterborne polyurethane, modified graphene oxide composite material, antibacterial nanocomposite material, filler component, silane coupling agent KH-560, dispersant, defoamer, thickener and leveling agent; The organosilicon-modified waterborne polyurethane is prepared by composite-modifying the waterborne polyurethane with epoxy resin and organosilicon, and the preparation steps are as follows: Step 1, add 5g of polypropylene glycol, 4g of dimethyl silicone oil and 10g of isophorone diisocyanate into a flask, stir at a stirring speed of 500r / min for 30min, then add 0.3g of dibutyltin dilaurate in a water bath at 70°C, stir at a stirring speed of 200r / min for 2h, and the resultant is recorded as a mixed component; Step 2, after cooling the mixed components to 50° C., 1.8 g of 1,4-butanediol, 2.2 g of 2,2-bis(hydroxymethyl)propionic acid and 8 g of acetone were added, and the mixture was stirred at a stirring speed of 300 r / min for 10 min, and then the temperature was raised to 70° C. and kept for reaction for 2 h. The obtained mixture was recorded as a silicone-modified waterborne polyurethane prepolymer; Step 3: add 2 g of epoxy resin to the silicone-modified waterborne polyurethane prepolymer, stir at a stirring speed of 200 r / min for 20 min, and react at a water bath temperature of 70°C for 2 h. Then, add 1 g of triethylamine and continue to react for 2 h. Then, add 15 g of deionized water and vigorously stir at a stirring speed of 600 r / min for 30 min to obtain the silicone-modified waterborne polyurethane.

[0020] The modified graphene oxide composite material is prepared by compounding p-phenylenediamine-modified graphene oxide and polyaniline, and the preparation steps are as follows: Step A, pour 0.5g of graphene oxide and 100mL of deionized water into a flask, add 1g of p-phenylenediamine and 1mL of ammonia water after ultrasonic dispersion at a frequency of 30kHz for 30min, stir and react at a water bath temperature of 90°C at a stirring speed of 200r / min for 3h, filter with a 0.22μm polytetrafluoroethylene filter paper, wash with anhydrous ethanol and deionized water three times in sequence, place in a freeze dryer and dry to obtain modified graphene oxide; Step B, add 2g of modified graphene oxide and 50mL of deionized water into a flask, mechanically stir at a stirring speed of 500r / min for 30min at room temperature, then add 1g of dodecylbenzenesulfonic acid, stir and emulsify at a stirring speed of 300r / min at a water bath temperature of 50°C for 30min, then add 1g of aniline and continue stirring for 10min, the result is recorded as the reaction component; Step C, placing the reaction components in an ice water bath at 0°C, adding a 10% ammonium persulfate aqueous solution at a drop rate of 1 drop / s until the color turns blue, then stopping the addition and stirring the reaction for 6 hours, filtering and removing the filtrate, washing with anhydrous ethanol and deionized water three times in sequence, and drying in a freeze dryer to obtain a modified graphene oxide composite material.

[0021] The antibacterial nanocomposite material is prepared by compounding copper oxide and silver ions, and the preparation steps are as follows: Step I, adding 0.8 g of natural honey to 50 mL of a 10 g / L copper acetate solution under vigorous stirring at a stirring speed of 800 r / min, adding 0.05 g of silver nitrate after continuing stirring at the original stirring speed for 10 min, and ultrasonically dispersing at a frequency of 30 kHz for 5 min, the result is recorded as the reaction system; Step II, place the reaction system in a water bath at 70°C, add 25mL of 10g / L sodium hydroxide solution, continue stirring at the original stirring speed for 1h, and then centrifuge at a speed of 10000r / min for 5min to obtain a precipitated product, wash the precipitated product three times with anhydrous ethanol and deionized water in sequence, and then place it in a vacuum drying oven at 60°C and dry it to constant weight, and the obtained antibacterial nanocomposite material is obtained.

[0022] The preparation method of the filler component is: 30 parts of water-reducing powder, 25 parts of iron oxide, 30 parts of mica powder, 35 parts of talcum powder, 40 parts of zinc phosphate and 50 parts of nano titanium dioxide are weighed by weight, poured into a mixer, and stirred and mixed at a stirring speed of 200 r / min to obtain the product.

[0023] A method for preparing an organosilicon-modified waterproof and anticorrosive coating, the preparation method comprising: S1, weighing 4 parts by weight of filler component and 1 part by weight of silane coupling agent KH-560 into a ball mill, adding 20 parts by weight of anhydrous ethanol, 5 parts by weight of modified graphene oxide composite material and 3 parts by weight of antibacterial nanocomposite material after ball milling for 10 minutes, stirring at a stirring speed of 500 r / min for 10 minutes, and recording the obtained mixture as filler mixed component; S2. Pour the filler mixture into 60 parts by weight of organosilicon-modified waterborne polyurethane, add 2 parts by weight of dispersant, 1 part by weight of defoamer, 1 part by weight of thickener and 2 parts by weight of leveling agent under stirring, and disperse ultrasonically at a frequency of 28 kHz for 30 minutes to obtain the organosilicon-modified waterproof and anticorrosive coating.

[0024] Embodiment 2: An organosilicon-modified waterproof and anticorrosive coating of this embodiment, the organosilicon-modified waterproof and anticorrosive coating is composed of the following components: organosilicon-modified waterborne polyurethane, modified graphene oxide composite material, antibacterial nanocomposite material, filler component, silane coupling agent KH-560, dispersant, defoamer, thickener and leveling agent; The organosilicon-modified waterborne polyurethane is prepared by composite-modifying the waterborne polyurethane with epoxy resin and organosilicon, and the preparation steps are as follows: Step 1, add 6g of polypropylene glycol, 5g of dimethyl silicone oil and 12g of isophorone diisocyanate into a flask, stir at a stirring speed of 500r / min for 30min, then add 0.4g of dibutyltin dilaurate in a water bath at 70°C, stir at a stirring speed of 200r / min for 2h, and the resultant is recorded as a mixed component; Step 2, after cooling the mixed components to 50° C., 2 g of 1,4-butanediol, 2.4 g of 2,2-bis(hydroxymethyl)propionic acid and 10 g of acetone were added, and the mixture was stirred at a stirring speed of 300 r / min for 10 min, and then the temperature was raised to 70° C. and kept for reaction for 2 h. The obtained mixture was recorded as a silicone-modified waterborne polyurethane prepolymer; Step 3: add 3 g of epoxy resin to the silicone-modified waterborne polyurethane prepolymer, stir at a stirring speed of 200 r / min for 20 min, and react at a water bath temperature of 70°C for 2 h. Then, add 2 g of triethylamine and continue to react for 2 h. Then, add 20 g of deionized water and vigorously stir at a stirring speed of 600 r / min for 30 min to obtain the silicone-modified waterborne polyurethane.

[0025] The modified graphene oxide composite material is prepared by compounding p-phenylenediamine-modified graphene oxide and polyaniline, and the preparation steps are as follows: Step A, pour 0.7g of graphene oxide and 100mL of deionized water into a flask, add 2g of p-phenylenediamine and 2mL of ammonia water after ultrasonic dispersion at a frequency of 30kHz for 30min, stir and react at a water bath temperature of 90°C at a stirring speed of 200r / min for 3h, filter with 0.22μm polytetrafluoroethylene filter paper, wash with anhydrous ethanol and deionized water three times in sequence, place in a freeze dryer and dry to obtain modified graphene oxide; Step B, add 3g of modified graphene oxide and 55mL of deionized water into a flask, stir mechanically at a stirring speed of 500r / min for 30min at room temperature, then add 2g of dodecylbenzenesulfonic acid, stir and emulsify at a stirring speed of 300r / min at a water bath temperature of 50°C for 30min, then add 2g of aniline and continue stirring for 10min, the result is recorded as the reaction component; Step C, placing the reaction components in an ice water bath at 0°C, adding a 10% ammonium persulfate aqueous solution at a drop rate of 1 drop / s until the color turns blue, then stopping the addition and stirring the reaction for 6 hours, filtering and removing the filtrate, washing with anhydrous ethanol and deionized water three times in sequence, and drying in a freeze dryer to obtain a modified graphene oxide composite material.

[0026] The antibacterial nanocomposite material is prepared by compounding copper oxide and silver ions, and the preparation steps are as follows: Step I, adding 1 g of natural honey to 50 mL of a 10 g / L copper acetate solution under vigorous stirring at a stirring speed of 800 r / min, adding 0.06 g of silver nitrate after continuing stirring at the original stirring speed for 10 min, and ultrasonically dispersing at a frequency of 30 kHz for 5 min, the result is recorded as the reaction system; Step II, place the reaction system in a water bath at 70°C, add 25mL of 10g / L sodium hydroxide solution, continue stirring at the original stirring speed for 1h, and then centrifuge at a speed of 10000r / min for 5min to obtain a precipitated product, wash the precipitated product three times with anhydrous ethanol and deionized water in sequence, and then place it in a vacuum drying oven at 60°C and dry it to constant weight, and the obtained antibacterial nanocomposite material is obtained.

[0027] The preparation method of the filler component is: 32 parts of water-reducing powder, 28 parts of iron oxide, 33 parts of mica powder, 36 parts of talcum powder, 42 parts of zinc phosphate and 55 parts of nano titanium dioxide were weighed by weight and poured into a mixer, and stirred and mixed at a stirring speed of 200 r / min to obtain the product.

[0028] A method for preparing an organosilicon-modified waterproof and anticorrosive coating, the preparation method comprising: S1, weigh 5 parts by weight of filler component and 2 parts by weight of silane coupling agent KH-560, pour them into a ball mill, ball mill for 10 minutes, add 25 parts by weight of anhydrous ethanol, parts by weight of modified graphene oxide composite material and 4 parts by weight of antibacterial nanocomposite material, stir at a stirring speed of 500 r / min for 10 minutes, and record the result as filler mixed component; S2. Pour the filler mixture into 80 parts by weight of organosilicon-modified waterborne polyurethane, add 3 parts by weight of dispersant, 2 parts by weight of defoamer, 3 parts by weight of thickener and 3 parts by weight of leveling agent under stirring, and disperse ultrasonically at a frequency of 30 kHz for 30 minutes to obtain the organosilicon-modified waterproof and anticorrosive coating.

[0029] Embodiment 3: An organosilicon-modified waterproof and anticorrosive coating of this embodiment, the organosilicon-modified waterproof and anticorrosive coating is composed of the following components: organosilicon-modified waterborne polyurethane, modified graphene oxide composite material, antibacterial nanocomposite material, filler component, silane coupling agent KH-560, dispersant, defoamer, thickener and leveling agent; The organosilicon-modified waterborne polyurethane is prepared by composite-modifying the waterborne polyurethane with epoxy resin and organosilicon, and the preparation steps are as follows: Step 1, add 6g of polypropylene glycol, 5g of dimethyl silicone oil and 11g of isophorone diisocyanate into a flask, stir at a stirring speed of 500r / min for 30min, then add 0.3 dibutyltin dilaurate in a water bath at 70°C, stir at a stirring speed of 200r / min for 2h, and the resultant is recorded as a mixed component; Step 2, after cooling the mixed components to 50° C., 1.9 g of 1,4-butanediol, 2.3 g of 2,2-bis(hydroxymethyl)propionic acid and 9 g of acetone were added, and the mixture was stirred at a stirring speed of 300 r / min for 10 min, and then the temperature was raised to 70° C. and kept for reaction for 2 h. The obtained mixture was recorded as a silicone-modified waterborne polyurethane prepolymer; Step 3: add 3 g of epoxy resin to the silicone-modified waterborne polyurethane prepolymer, stir at a stirring speed of 200 r / min for 20 min, and react at a water bath temperature of 70°C for 2 h. Then, add 2 g of triethylamine and continue to react for 2 h. Then, add 18 g of deionized water and vigorously stir at a stirring speed of 600 r / min for 30 min to obtain the silicone-modified waterborne polyurethane.

[0030] The modified graphene oxide composite material is prepared by compounding p-phenylenediamine-modified graphene oxide and polyaniline, and the preparation steps are as follows: Step A, pour 0.6g of graphene oxide and 100mL of deionized water into a flask, add 2g of p-phenylenediamine and 1mL of ammonia water after ultrasonic dispersion at a frequency of 30kHz for 30min, stir and react at a water bath temperature of 90°C at a stirring speed of 200r / min for 3h, filter with a 0.22μm polytetrafluoroethylene filter paper, wash with anhydrous ethanol and deionized water three times in sequence, and place in a freeze dryer to dry to obtain modified graphene oxide; Step B, add 3g of modified graphene oxide and 53mL of deionized water into a flask, mechanically stir at a stirring speed of 500r / min for 30min at room temperature, then add 2g of dodecylbenzenesulfonic acid, stir and emulsify at a stirring speed of 300r / min at a water bath temperature of 50°C for 30min, then add 2g of aniline and continue stirring for 10min, the result is recorded as the reaction component; Step C, placing the reaction components in an ice water bath at 0°C, adding a 10% ammonium persulfate aqueous solution at a drop rate of 1 drop / s until the color turns blue, then stopping the addition and stirring the reaction for 6 hours, filtering and removing the filtrate, washing with anhydrous ethanol and deionized water three times in sequence, and drying in a freeze dryer to obtain a modified graphene oxide composite material.

[0031] The antibacterial nanocomposite material is prepared by compounding copper oxide and silver ions, and the preparation steps are as follows: Step I, adding 0.9 g of natural honey to 50 mL of a 10 g / L copper acetate solution under vigorous stirring at a stirring speed of 800 r / min, adding 0.06 g of silver nitrate after continuing stirring at the original stirring speed for 10 min, and ultrasonically dispersing at a frequency of 30 kHz for 5 min, the result is recorded as the reaction system; Step II, place the reaction system in a water bath at 70°C, add 25mL of 10g / L sodium hydroxide solution, continue stirring at the original stirring speed for 1h, and then centrifuge at a speed of 10000r / min for 5min to obtain a precipitated product, wash the precipitated product three times with anhydrous ethanol and deionized water in sequence, and then place it in a vacuum drying oven at 60°C and dry it to constant weight, and the obtained antibacterial nanocomposite material is obtained.

[0032] The preparation method of the filler component is: 31 parts of water-reducing powder, 27 parts of iron oxide red, 32 parts of mica powder, 35 parts of talcum powder, 41 parts of zinc phosphate and 53 parts of nano titanium dioxide were weighed by weight and poured into a mixer, and stirred and mixed at a stirring speed of 200 r / min to obtain the product.

[0033] A method for preparing an organosilicon-modified waterproof and anticorrosive coating, the preparation method comprising: S1, weigh 5 parts by weight of filler component and 2 parts by weight of silane coupling agent KH-560, pour them into a ball mill, add 23 parts by weight of anhydrous ethanol, 6 parts by weight of modified graphene oxide composite material and 3 parts by weight of antibacterial nanocomposite material after ball milling for 10 minutes, stir at a stirring speed of 500 r / min for 10 minutes, and record the result as filler mixed component; S2. Pour the filler mixture into 70 parts by weight of organosilicon-modified waterborne polyurethane, add 3 parts by weight of dispersant, 2 parts by weight of defoamer, 1 part by weight of thickener and 3 parts by weight of leveling agent under stirring, and disperse ultrasonically at a frequency of 29 kHz for 30 minutes to obtain the organosilicon-modified waterproof and anticorrosive coating.

[0034] Comparative Example 1: The organosilicon-modified waterproof and anti-corrosion coating and its preparation method provided in this comparative example are roughly the same as those in Example 1, with the main difference being that in this comparative example 1, the organosilicon-modified waterborne polyurethane in Example 1 is replaced by a waterborne polyurethane with model number CN-855.

[0035] Comparative Example 2: The organosilicon-modified waterproof and anticorrosive coating and its preparation method provided in this comparative example are roughly the same as those in Example 1, with the main difference being that in this comparative example 1, the modified graphene oxide composite material in Example 1 is replaced with graphene oxide prepared by the Hummer method.

[0036] Comparative Example 3: The organosilicon-modified waterproof and anticorrosive coating and its preparation method provided in this comparative example are substantially the same as those in Example 1, with the main difference being that the antibacterial nanocomposite material in Example 1 is replaced with copper oxide in this comparative example.

[0037] Performance Testing: The organosilicon modified waterproof and anticorrosive coatings prepared in Examples 1-3 and Comparative Examples 1-3 are marked as Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3, respectively, and then the performance of Examples 1-3 and Comparative Examples 1-3 is tested, and the specific testing methods and test items are as follows: 1. Referring to the standards of GB / T9274-1988 and GB / T1771-2007, the acid and alkali corrosion resistance and salt spray corrosion resistance of Examples 1-3 and Comparative Examples 1-3 were tested, and the obtained data are recorded in Table 1; 2. Referring to the standard of HG / T3344-2012, the water absorption of Examples 1-3 and Comparative Examples 1-3 was tested, and the obtained water absorption data were recorded in Table 2; 3. Referring to the standard of GB / T1732-1993, the impact resistance of Examples 1-3 and Comparative Examples 1-3 was tested, and the obtained data are recorded in Table 2; 4. Referring to the standard of GB / T2591-2003, the antibacterial properties of Examples 1-3 and Comparative Examples 1-3 were tested, and the data of the comprehensive antibacterial rates were recorded in Table 2; Table 1: Test data of acid and alkali corrosion resistance and salt spray corrosion resistance of different coatings

[0038] Table 2: Data table of water absorption, impact resistance and comprehensive antibacterial rate of different coatings

[0039] It can be seen from the data in Tables 1 and 2 that the corrosion resistance and water resistance of the organosilicon modified waterproof and anti-corrosion coatings in Examples 1-3 are significantly better than those in Comparative Examples 1-2, indicating that the addition of organosilicon modified waterborne polyurethane and modified graphene oxide composite materials in the preparation of organosilicon modified waterproof and anti-corrosion coatings can improve the corrosion resistance and water resistance of the coatings. The antibacterial property of the organosilicon modified waterproof and anti-corrosion coatings in Examples 1-3 is significantly better than that in Comparative Example 3, indicating that the addition of antibacterial nanocomposites to organosilicon modified waterproof and anti-corrosion coatings can improve the antibacterial properties.

[0040] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the presence of other identical elements in the process, method, article or device including the elements.

[0041] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An organosilicon-modified waterproof and anticorrosive coating, characterized in that: The organosilicon-modified waterproof and anticorrosive coating is composed of the following components: organosilicon-modified waterborne polyurethane, modified graphene oxide composite material, antibacterial nanocomposite material, filler component, silane coupling agent KH-560, dispersant, defoamer, thickener and leveling agent; The organosilicon-modified waterborne polyurethane is prepared by composite-modifying the waterborne polyurethane with epoxy resin and organosilicon; The modified graphene oxide composite material is prepared by compounding p-phenylenediamine-modified graphene oxide and polyaniline; The antibacterial nano composite material is prepared by compounding copper oxide and silver ions.

2. The organosilicon-modified waterproof and anticorrosive coating according to claim 1, characterized in that: The preparation steps of the organosilicon-modified waterborne polyurethane are as follows: Step 1, add 5-6g of polypropylene glycol, 4-5g of dimethyl silicone oil and 10-12g of isophorone diisocyanate into a flask, mix well, add 0.3-0.4g of dibutyltin dilaurate in a water bath at 70°C, stir and react for 2h, and record the result as a mixed component; Step 2, after cooling the mixed components to 50° C., 1.8-2 g of 1,4-butanediol, 2.2-2.4 g of 2,2-bis(hydroxymethyl)propionic acid and 8-10 g of acetone are added, and after stirring and dispersing, the temperature is raised to 70° C. and kept for reaction for 2 hours. The obtained product is recorded as a silicone-modified waterborne polyurethane prepolymer; Step 3: add 2-3 g of epoxy resin to the organosilicon-modified waterborne polyurethane prepolymer, stir and mix, and react in a water bath at 70° C. for 2 h. Then, add 1-2 g of triethylamine and continue to react for 2 h. Then, add 15-20 g of deionized water and stir vigorously for 30 min. The result is the organosilicon-modified waterborne polyurethane.

3. The organosilicon-modified waterproof and anticorrosive coating according to claim 2, characterized in that: The specific operation of uniform mixing in step 1 is stirring at a stirring speed of 500 r / min for 30 min, the stirring speed of the stirring reaction in step 1 is 200 r / min, the specific operation of stirring and dispersing in step 2 is stirring at a stirring speed of 300 r / min for 10 min, the specific operation of stirring and mixing in step 3 is stirring at a stirring speed of 200 r / min for 20 min, and the stirring speed of the vigorous stirring in step 3 is 600 r / min.

4. The organosilicon-modified waterproof and anticorrosive coating according to claim 1, characterized in that: The preparation steps of the modified graphene oxide composite material are: Step A, pour 0.5-0.7g of graphene oxide and 100mL of deionized water into a flask, add 1-2g of p-phenylenediamine and 1-2mL of ammonia water after ultrasonic treatment, stir and react at a water bath temperature of 90°C for 3h, filter with 0.22μm polytetrafluoroethylene filter paper, wash with anhydrous ethanol and deionized water three times in sequence, place in a freeze dryer and dry to obtain modified graphene oxide; Step B, add 2-3g of modified graphene oxide and 50-55mL of deionized water into a flask, add 1-2g of dodecylbenzenesulfonic acid after mechanical stirring at room temperature for 30min, stir and emulsify at a water bath temperature of 50°C for 30min, add 1-2g of aniline and continue stirring for 10min, the result is recorded as the reaction component; Step C, placing the reaction components in an ice water bath at 0°C, adding a 10% by mass fraction of ammonium persulfate aqueous solution until the color turns blue, then stopping the addition and stirring the reaction for 6 hours, filtering and removing the filtrate, washing with anhydrous ethanol and deionized water three times in sequence, and drying in a freeze dryer to obtain a modified graphene oxide composite material.

5. The organosilicon-modified waterproof and anticorrosive coating according to claim 4, characterized in that: The specific operation of the ultrasonic treatment in step A is ultrasonic dispersion at a frequency of 30 kHz for 30 min, the stirring speed of the stirring reaction in step A is 200 r / min, the stirring speed of the mechanical stirring in step B is 500 r / min, the stirring speed of the stirring emulsification in step B is 300 r / min, and the dripping rate in step C is 1 drop / s.

6. The organosilicon-modified waterproof and anticorrosive coating according to claim 1, characterized in that: The preparation steps of the antibacterial nanocomposite material are as follows: Step I, adding 0.8-1 g of natural honey to 50 mL of 10 g / L copper acetate solution under vigorous stirring, continuing stirring at the original stirring speed for 10 min, adding 0.05-0.06 g of silver nitrate and performing ultrasonic treatment, the result is recorded as the reaction system; Step II, place the reaction system in a water bath at 70°C, add 25mL of 10g / L sodium hydroxide solution, continue stirring at the original stirring speed for 1h, and then centrifuge to obtain a precipitated product. Wash the precipitated product three times with anhydrous ethanol and deionized water in sequence, and then dry it to obtain an antibacterial nanocomposite material.

7. The organosilicon-modified waterproof and anticorrosive coating according to claim 6, characterized in that: The stirring speed of the vigorous stirring condition in step I is 800 r / min, the specific operation of the ultrasonic treatment in step I is ultrasonic dispersion at a frequency of 30 kHz for 5 minutes, the specific operation of the centrifugal treatment in step II is centrifugation at a speed of 10000 r / min for 5 minutes, and the specific operation of the drying treatment in step II is drying in a vacuum drying oven at 60° C. to constant weight.

8. The organosilicon-modified waterproof and anticorrosive coating according to claim 1, characterized in that: The preparation method of the filler component is: 30-32 parts of water-reducing powder, 25-28 parts of iron oxide red, 30-33 parts of mica powder, 35-36 parts of talc powder, 40-42 parts of zinc phosphate and 50-55 parts of nano titanium dioxide are weighed by weight, poured into a mixer, and stirred and mixed at a stirring speed of 200 r / min to obtain the product.

9. A method for preparing an organosilicon-modified waterproof and anticorrosive coating according to any one of claims 1 to 8, characterized in that: The preparation method is: S1, weighing 4-5 parts by weight of filler component and 1-2 parts by weight of silane coupling agent KH-560 into a ball mill, adding 20-25 parts by weight of anhydrous ethanol, 5-6 parts by weight of modified graphene oxide composite material and 3-4 parts by weight of antibacterial nanocomposite material after ball milling for 10 minutes, stirring and dispersing uniformly, and recording the obtained mixture as filler mixed component; S2. Pour the filler mixture into 60-80 parts by weight of organosilicon-modified waterborne polyurethane, add 2-3 parts by weight of dispersant, 1-2 parts by weight of defoamer, 1-3 parts by weight of thickener and 2-3 parts by weight of leveling agent under stirring, and obtain the organosilicon-modified waterproof and anticorrosive coating after ultrasonic treatment.

10. The method for preparing a silicone-modified waterproof and anticorrosive coating according to claim 9, characterized in that: The specific operation of stirring and dispersing uniformly in S1 is stirring at a stirring speed of 500 r / min for 10 min, and the specific operation of ultrasonic treatment in S2 is ultrasonic dispersion at a frequency of 28-30 kHz for 30 min.

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