Power tower rust-proof and corrosion-proof paint and preparation method thereof

Abstract

The application provides a power iron tower rust-proof and corrosion-resistant paint and a preparation method thereof, and belongs to the technical field of paints. Modified waterborne polyurethane is prepared from white bark pine alcohol and modified polyurethane of piceatannol, modified graphene oxide of polydopamine is prepared, is added into epoxy resin together with nano silicon dioxide to prepare modified epoxy resin emulsion, mesoporous nano zinc molybdate / zinc phosphate is prepared and is modified by a silane coupling agent on the surface, the modified waterborne polyurethane, the modified epoxy resin emulsion, a pH value regulator, a dispersing agent, a defoaming agent, pigments, talcum powder and water are stirred and uniformly mixed, a thickening agent is added, stirring is uniformly carried out, filtration is carried out, and the power iron tower rust-proof and corrosion-resistant paint is prepared. Through physical and chemical synergistic corrosion protection, the corrosion resistance of the paint is improved. Meanwhile, the paint is water-based, green and environmentally-friendly, has good flexibility, impact resistance, chemical solvent resistance, weather resistance, salt spray resistance and rust resistance, and has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of paint technology, in particular to a rust and corrosion resistant coating for electric power towers and a preparation method thereof. BACKGROUND

[0002] Electric power towers are prone to corrosion due to long-term exposure to various environmental conditions, so rust and corrosion resistant coatings are needed to extend their service life. According to search results, Shandong Electric Power Research Institute has developed a new type of rust and corrosion resistant coating.

[0003] Corrosion resistant coatings should be classified as functional (special) coatings. Since the liberation, China has attached great importance to corrosion resistant coatings, and their development has gone through three periods. In the first period, oil-based resins, alkyd resins, and phenolic resins were used as binders, and red lead and other lead and chromium-containing pigments were used as rust inhibitors. This period lasted until the 1960s. After that, synthetic resins were developed. In addition to the above-mentioned binders, epoxy, chlorinated rubber, ethylene resin, chlorosulfonated polyethylene, and silicate were also used. Non-toxic varieties such as zinc powder, aluminum powder, zinc phosphate, barium metaborate, and red iron oxide were also used as corrosion resistant pigments. Rheological additives began to be used in corrosion resistant coatings, and heavy-duty corrosion resistant coatings, wet adhesion theory, and barrier principles were also applied in corrosion resistant coatings. Due to the increasing strictness of environmental protection requirements, replacing the original binders that pollute the atmosphere and toxic rust-inhibiting pigments that harm the environment has become the main direction for developing new corrosion resistant coatings. At the same time, various industries and construction fields have put forward new requirements for corrosion resistant coatings, especially heavy-duty corrosion resistant coatings. These requirements include high performance, economy, suitability for poor substrates or rusted surfaces, no heavy metals, high solids, water-based or solvent-free, ultra-thick film, odorless, corrosion and decorative, acid rain resistance, multifunctional, energy-saving, etc. These are the main goals of the development of corrosion resistant coatings in China. SUMMARY

[0004] The purpose of the present application is to provide a rust and corrosion resistant coating for electric power towers and a preparation method thereof. Through physical and chemical synergistic corrosion protection, the corrosion resistance of the coating is improved. At the same time, the coating is water-based, environmentally friendly, flexible, impact-resistant, chemical solvent-resistant, weather-resistant, salt spray-resistant, and has good rust resistance, making it suitable for a wide range of applications.

[0005] The technical solution of the present application is as follows:

[0006] The application provides a preparation method of a power iron tower rust-proof and corrosion-resistant paint, and the method comprises the following steps: modifying white bark pine alcohol and white wine to prepare modified waterborne polyurethane; modifying polydopamine to prepare modified graphene oxide; adding the modified graphene oxide and nano silicon dioxide into epoxy resin to prepare modified epoxy resin emulsion; preparing mesoporous nano zinc molybdate / zinc phosphate and modifying the surface of the mesoporous nano zinc molybdate / zinc phosphate by a silane coupling agent; stirring and uniformly mixing the modified waterborne polyurethane, the modified epoxy resin emulsion, a pH regulator, a dispersing agent, a defoaming agent, pigments, talcum powder and water; colloid milling; adding a thickening agent and uniformly stirring; filtering; and preparing the power iron tower rust-proof and corrosion-resistant paint.

[0007] As a further improvement of the application, the following steps are included:

[0008] S1. Preparation of a modifier: uniformly mixing white bark pine alcohol and white wine to prepare the modifier;

[0009] S2. Preparation of modified waterborne polyurethane: adding polytetrahydrofuran diol into acetone, heating, dropwise adding isocyanate, stirring and reacting, adding a catalyst, dimethylol propionic acid, 1,4-butanediol and the modifier, continuously stirring and reacting, reducing to room temperature, adding triethylamine, stirring and reacting, adding deionized water, emulsifying, removing acetone under reduced pressure, and preparing the modified waterborne polyurethane;

[0010] S3. Preparation of modified graphene oxide: dissolving graphene oxide in water, adding dopamine hydrochloride and a catalyst, heating and stirring and reacting, and drying to prepare the modified graphene oxide;

[0011] S4. Preparation of modified epoxy resin emulsion: mixing polyethylene glycol and multifunctional epoxy resin, adding boron trifluoride ether, heating and stirring and reacting to prepare an emulsifier, adding the emulsifier and the epoxy resin into water, heating and stirring and reacting, then adding the modified graphene oxide and nano silicon dioxide, stirring and reacting, colloid milling, and preparing the modified epoxy resin emulsion;

[0012] S5. Preparation of mesoporous nano zinc molybdate / zinc phosphate: dissolving ammonium molybdate and ammonium phosphate in water, adding ethanol and polyethylene glycol, stirring and uniformly mixing, dropwise adding a zinc chloride solution, then adding polyvinyl alcohol, heating and stirring and reacting, centrifuging, washing, drying, and preparing the mesoporous nano zinc molybdate / zinc phosphate;

[0013] S6. Preparation of modified mesoporous nano zinc molybdate / zinc phosphate: adding the mesoporous nano zinc molybdate / zinc phosphate into ethanol, adding a silane coupling agent, heating and stirring and reacting, and preparing the modified mesoporous nano zinc molybdate / zinc phosphate;

[0014] S7. Preparation of the rust-proof and corrosion-proof coating for power iron tower: the modified waterborne polyurethane, the modified epoxy resin emulsion, the pH value regulator, the dispersing agent, the defoaming agent and water are stirred and mixed uniformly, the modified mesoporous nano zinc molybdate / zinc phosphate, the pigment and the talc are added, the colloidal mill is used, the thickening agent is added, stirring is uniformly conducted, filtration is conducted, and thus the rust-proof and corrosion-proof coating for power iron tower is prepared.

[0015] As a further improvement of the present application, the mass ratio of the piceatannol and the resveratrol in step S1 is 3-5:2-3.

[0016] As a further improvement of the present application, the mass ratio of the polytetrahydrofuran diol, the isocyanate, the catalyst, the dimethylol propionic acid, the 1,4-butanediol, the modifier and the triethylamine in step S2 is 10:5-7:0.01-0.02:1-2:0.2-0.4:2-4:0.5-1.5, the heating is to a temperature of 55-65℃, the isocyanate is at least one selected from isophorone diisocyanate, toluene diisocyanate, diphenyl methane diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, the catalyst is dibutyl tin dilaurate or stannous octoate, and the emulsifying time is 20-30min.

[0017] As a further improvement of the present application, the mass ratio of the graphene oxide, the dopamine hydrochloride and the catalyst in step S3 is 10:3-6:0.1-0.2, the heating and stirring reaction is at a temperature of 40-50℃ for 2-4h, and the catalyst is a Tris-HCl solution with a pH value of 8.5-9.5.

[0018] As a further improvement of the present application, the mass ratio of the polyethylene glycol, the multifunctional epoxy resin and the boron trifluoride etherate in step S4 is 3-5:4-7:0.5-1, the multifunctional epoxy resin is epoxy resin DEN-425, the mass ratio of the emulsifier, the epoxy resin, the modified graphene oxide and the nano silicon dioxide is 2-4:60-80:4-7:1-2, the rotation speed of the colloidal mill is 10000-12000r / min for 1-3h, and the epoxy resin is a bisphenol A or bisphenol F type epoxy resin.

[0019] As a further improvement of the present application, the mass ratio of the ammonium molybdate, the ammonium phosphate, the ethanol, the polyethylene glycol, the zinc chloride and the polyvinyl alcohol in step S5 is 1.9-2.0:1.4-1.5:10-15:0.3-0.5:2.6-2.8:0.1-0.2, the heating and stirring reaction is at a temperature of 55-65℃ for 1-2h.

[0020] As a further improvement of the present application, the mass ratio of the mesoporous zinc molybdate / zinc phosphate in step S6 and the silane coupling agent is 10:1-2, the silane coupling agent is selected from at least one of KH550, KH692 and KH702, the temperature of the heating and stirring reaction is 40-50 DEG C, and the time is 1-3h.

[0021] As a further improvement of the present application, the mass ratio of the modified waterborne polyurethane, modified epoxy resin emulsion, pH value regulator, dispersant, defoaming agent, water, modified mesoporous zinc molybdate / zinc phosphate, pigment, talc powder and thickening agent in step S7 is 30-40:7-10:1-2:0.2-0.4:0.1-0.2:20-40:3-4:1-3:1-2:0.5-1, the pH value regulator is N,N-dimethyl ethanol, the dispersant is 104BC, the defoaming agent is BYK-024, the pigment is carbon black, and the thickening agent is polyurethane RM-8W.

[0022] The present application further protects a power iron tower anti-rust and anti-corrosion coating prepared by the above preparation method.

[0023] The present application has the following beneficial effects:

[0024] Compared with traditional solvent-based polyurethane coatings, the waterborne polyurethane coatings have poor water resistance, chemical reagent resistance, heat resistance and fullness, the present application uses coniferyl alcohol and piceatannol as internal crosslinking modifiers, which have conjugated double bonds and hydroxyl structures, can react with isocyanate to form branched polyurethane segments, play the role of internal crosslinking agent, and the conjugated double bonds can be oxidized and crosslinked to form a film, so that the waterborne emulsion has better film forming property, and the waterborne polyurethane anti-corrosion coating film has better water resistance, acid and alkali resistance and salt spray resistance.

[0025] Compared with polyurethane, silicone and other resins, epoxy resin has more excellent anti-corrosion protection effect, but has deficiencies in toughness and impact resistance. Graphene is a new two-dimensional nanomaterial, which has excellent electrical conductivity, flexibility and physical shielding performance for water molecules and air. However, the aggregation of graphene makes it difficult to uniformly disperse in the epoxy resin emulsion. The present application modifies graphene oxide by polydopamine, the amino groups on the surface of the graphene oxide can react with the residual epoxy groups of the epoxy resin, improving the dispersibility of the graphene oxide, solving the aggregation problem caused by physical blending of graphene, and realizing the physical shielding effect of the coating layer with a small amount of graphene, and greatly improving the flexibility, electrical conductivity and impact resistance of the coating.

[0026] Zinc phosphate is a kind of environment-friendly anti-rust pigment with excellent performance, but ordinary zinc phosphate has large particle size, small specific surface area, low solubility in water, poor hydrolysis and slow forming speed of passivation protective film in the early stage of corrosion, thereby affecting the overall anti-rust performance of the coating. The present application also prepares a mesoporous nano zinc molybdate / zinc phosphate, which greatly reduces the particle size of the product, and the mesoporous structure and nano-sized particles increase the specific surface area thereof. Further modification by a silane coupling agent with amino groups is carried out, and the prepared product can react with isocyanate and residual groups of epoxy resin, thereby improving the dispersibility of the product, avoiding adverse effects on the mechanical properties, and at the same time, making zinc phosphate and zinc molybdate produce local anode and cathode on the surface of steel in the early stage of corrosion. Zinc phosphate makes dissolved iron salt and ferrous salt hydrolyze, and the released protons produce zinc ions and phosphoric acid with zinc phosphate, and the zinc ions and iron ions form a hardly soluble complex Fe[Zn3(PO4)] to play a cathodic protection role. Zinc molybdate not only forms a complex with iron ions to play an anodic passivation role, but also produces molybdate that can react with iron rust to form a heteropoly acid complex to stabilize the iron rust. In addition, the presence of molybdenum ions can increase the polarization resistance of the steel surface, reduce the critical current density required for passivation and increase the stability of the passivation film.

[0027] Therefore, the modified mesoporous nano zinc molybdate / zinc phosphate of the present application selects a modified mesoporous nano zinc molybdate / zinc phosphate with an electrochemical protection function, and further adds an epoxy resin modified by graphene oxide to achieve the purpose of improving the corrosion resistance of the coating through physical and chemical synergistic corrosion protection. The addition of nano-silicon dioxide can improve the adhesion of the coating through inorganic-inorganic interaction, and also improve the mechanical properties of the coating.

[0028] The power iron tower anti-rust and anticorrosion coating prepared by the present application achieves the purpose of improving the corrosion resistance of the coating through physical and chemical synergistic corrosion protection. At the same time, the coating is a water-based coating, which is green and environmentally friendly, has good flexibility, impact resistance, chemical solvent resistance, weather resistance, salt spray resistance and rust resistance, and has a wide application prospect. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0030] The dispersant 104BC is a Korean KS Rheorlow DW-104BC dispersant.

[0031] The polyurethane RM-8W is a Rohm & Haas thickening agent RM8W.

[0032] Epoxy resin DEN-425 is Dow phenolic epoxy resin DEN 425.

[0033] Example 1

[0034] The embodiment provides a preparation method of a rust-proof and corrosion-proof coating for a power iron tower, and comprises the following steps:

[0035] S1. Preparation of a modifier: 3 g of coniferyl alcohol and 2 g of piceatannol are stirred and mixed for 10 min to obtain the modifier;

[0036] S2. Preparation of modified waterborne polyurethane: 10 g of polytetrahydrofuran diol 2000 is added into 50 mL of acetone, heated to 55 ℃, 5 g of toluene diisocyanate is added dropwise, stirred and reacted for 1 h, 0.01 g of dibutyltin dilaurate, 1 g of dimethylol propionic acid, 0.2 g of 1,4-butanediol and 2 g of the modifier are added, and stirring and reaction are continued for 5 h, and then the temperature is reduced to room temperature, 0.5 g of triethylamine is added, stirring and reaction are continued for 30 min, 30 mL of deionized water is added, emulsification is performed for 20 min, and then acetone is removed under reduced pressure to obtain the modified waterborne polyurethane;

[0037] S3. Preparation of modified graphene oxide: 1 g of graphene oxide is dissolved in 1000 mL of water, 0.3 g of dopamine hydrochloride and 0.01 g of a catalyst are added, heated to 40 ℃, and stirring and reaction are continued for 2 h, and then drying is performed to obtain the modified graphene oxide;

[0038] The catalyst is a Tris-HCl solution with pH=8.5;

[0039] S4. Preparation of modified epoxy resin emulsion: 3 g of polyethylene glycol 400 and 4 g of epoxy resin DEN-425 are mixed, 0.5 g of boron trifluoride etherate is added, heated to 85 ℃, and stirring and reaction are continued for 3 h to obtain an emulsifier, 2 g of the emulsifier and 60 g of bisphenol F type epoxy resin are added into 500 mL of water, heated to 70 ℃, and stirring and reaction are continued for 1 h, then 4 g of the modified graphene oxide and 1 g of nano silicon dioxide are added, stirring and reaction are continued for 1 h, and then 10000 r / min colloidal mill is used for 1 h to obtain the modified epoxy resin emulsion;

[0040] S5. Preparation of mesoporous nano zinc molybdate / zinc phosphate: 1.9 g of ammonium molybdate and 1.4 g of ammonium phosphate are dissolved in 200 mL of water, 10 g of ethanol and 0.3 g of polyethylene glycol 400 are added, stirring and mixing are performed for 30 min, 100 mL of a solution containing 2.6 g of zinc chloride is added dropwise, then 0.1 g of polyvinyl alcohol is added, heated to 55 ℃, and stirring and reaction are continued for 1 h, and then centrifugation, washing and drying are performed to obtain the mesoporous nano zinc molybdate / zinc phosphate;

[0041] S6. Preparation of modified mesoporous zinc molybdate / zinc phosphate nanoparticles: 10 g of mesoporous zinc molybdate / zinc phosphate nanoparticles were added to 200 mL of ethanol, 1 g of silane coupling agent KH692 was added, heated to 40℃, and stirred for 1 h to obtain modified mesoporous zinc molybdate / zinc phosphate nanoparticles;

[0042] S7. Preparation of power tower rust-proof and corrosion-resistant paint: 30 g of modified waterborne polyurethane, 7 g of modified epoxy resin emulsion, 1 g of N, N-dimethyl ethanol, 0.2 g of dispersant 104BC, 0.1 g of defoamer BYK-024, and 20 mL of water were stirred and mixed uniformly, 3 g of modified mesoporous zinc molybdate / zinc phosphate nanoparticles, 1 g of carbon black, and 1 g of talc were added, and 10000 r / min colloidal mill was used for 1 h, 0.5 g of polyurethane RM-8W was added, stirred for 20 min, filtered, and power tower rust-proof and corrosion-resistant paint was prepared.

[0043] Example 2

[0044] The embodiment provides a preparation method of power tower rust-proof and corrosion-resistant paint, which comprises the following steps:

[0045] S1. Preparation of modifier: 5 g of pinoresinol and 3 g of piceatannol were stirred and mixed for 10 min to obtain a modifier;

[0046] S2. Preparation of modified waterborne polyurethane: 10 g of polytetrahydrofuran diol 2000 was added to 50 mL of acetone, heated to 65℃, 7 g of toluene diisocyanate was added dropwise, stirred for 1 h, 0.02 g of dibutyltin dilaurate, 2 g of dimethylol propionic acid, 0.4 g of 1, 4-butanediol, and 4 g of the modifier were added, and the stirring reaction was continued for 5 h, and then the temperature was lowered to room temperature, 1.5 g of triethylamine was added, stirred for 30 min, 30 mL of deionized water was added, emulsified for 30 min, and then acetone was removed under reduced pressure to obtain modified waterborne polyurethane;

[0047] S3. Preparation of modified graphene oxide: 1 g of graphene oxide was dissolved in 1000 mL of water, 0.6 g of dopamine hydrochloride and 0.02 g of catalyst were added, heated to 50℃, and stirred for 4 h to obtain modified graphene oxide;

[0048] The catalyst is Tris-HCl solution with pH = 9.5;

[0049] S4. Preparation of modified epoxy resin emulsion: 5 g of polyethylene glycol 400 and 7 g of epoxy resin DEN-425 are mixed, 1 g of boron trifluoride ether is added, heated to 95°C, stirred for 5 h, and an emulsifier is prepared. 4 g of the emulsifier and 80 g of bisphenol A type epoxy resin are added to 500 mL of water, heated to 80°C, stirred for 2 h, then 7 g of modified graphene oxide and 2 g of nano silicon dioxide are added, stirred for 2 h, and 12000 r / min colloidal mill is used for 3 h to prepare the modified epoxy resin emulsion;

[0050] S5. Preparation of mesoporous zinc molybdate / zinc phosphate nanoparticles: 2.0 g of ammonium molybdate and 1.5 g of ammonium phosphate are dissolved in 200 mL of water, 15 g of ethanol and 0.5 g of polyethylene glycol 400 are added, stirred and mixed for 30 min, 100 mL of a solution containing 2.8 g of zinc chloride is added dropwise, then 0.2 g of polyvinyl alcohol is added, heated to 65°C, stirred for 2 h, centrifuged, washed and dried to obtain mesoporous zinc molybdate / zinc phosphate nanoparticles;

[0051] S6. Preparation of modified mesoporous zinc molybdate / zinc phosphate nanoparticles: 10 g of mesoporous zinc molybdate / zinc phosphate nanoparticles are added to 200 mL of ethanol, 2 g of silane coupling agent KH702 is added, heated to 50°C, stirred for 3 h, and the modified mesoporous zinc molybdate / zinc phosphate nanoparticles are obtained.

[0052] S7. Preparation of power tower anti-rust and anti-corrosion coating: 40 g of modified waterborne polyurethane, 10 g of modified epoxy resin emulsion, 2 g of N,N-dimethyl ethanol, 0.4 g of dispersant 104BC, 0.2 g of defoamer BYK-024 and 40 mL of water are stirred and mixed uniformly, 4 g of modified mesoporous zinc molybdate / zinc phosphate, 3 g of carbon black and 2 g of talc powder are added, 12000 r / min colloidal mill is used for 1 h, 1 g of polyurethane RM-8W is added, stirred for 20 min, filtered, and the power tower anti-rust and anti-corrosion coating is obtained.

[0053] Example 3

[0054] The embodiment provides a preparation method of a power tower anti-rust and anti-corrosion coating, which comprises the following steps:

[0055] S1. Preparation of modifier: 4 g of pinoresinol and 2.5 g of piceatannol are stirred and mixed for 10 min to obtain the modifier.

[0056] S2. Preparation of modified waterborne polyurethane: 10 g of polytetrahydrofuran diol 2000 was added to 50 mL of acetone, heated to 60°C, 6 g of toluene diisocyanate was added dropwise, stirred for 1 h, 0.015 g of dibutyltin dilaurate, 1.5 g of dimethylol propionic acid, 0.3 g of 1,4-butanediol and 3 g of modifier were added, and the reaction was continued for 5 h with stirring, and then the temperature was lowered to room temperature, 1 g of triethylamine was added, and the reaction was stirred for 30 min, 30 mL of deionized water was added, emulsified for 25 min, and then the acetone was removed under reduced pressure to obtain the modified waterborne polyurethane;

[0057] S3. Preparation of modified graphene oxide: 1 g of graphene oxide was dissolved in 1000 mL of water, 0.45 g of dopamine hydrochloride and 0.015 g of catalyst were added, heated to 45°C, stirred for 3 h, and then dried to obtain the modified graphene oxide;

[0058] The catalyst is Tris-HCl solution with pH = 9;

[0059] S4. Preparation of modified epoxy resin emulsion: 4 g of polyethylene glycol 400 and 5.5 g of epoxy resin DEN-425 were mixed, 0.7 g of boron trifluoride ether was added, heated to 90°C, stirred for 4 h to obtain the emulsifier, 3 g of the emulsifier and 70 g of bisphenol A type epoxy resin were added to 500 mL of water, heated to 75°C, stirred for 1.5 h, then 5.5 g of modified graphene oxide and 1.5 g of nano silica were added, stirred for 1.5 h, and then the mixture was subjected to 11000 r / min colloid mill for 2 h to obtain the modified epoxy resin emulsion;

[0060] S5. Preparation of mesoporous zinc molybdate / zinc phosphate nanoparticles: 1.96 g of ammonium molybdate and 1.46 g of ammonium phosphate were dissolved in 200 mL of water, 12 g of ethanol and 0.4 g of polyethylene glycol 400 were added, stirred and mixed for 30 min, 100 mL of a solution containing 2.74 g of zinc chloride was added dropwise, then 0.15 g of polyvinyl alcohol was added, heated to 60°C, stirred for 1.5 h, centrifuged, washed, and dried to obtain the mesoporous zinc molybdate / zinc phosphate nanoparticles;

[0061] S6. Preparation of modified mesoporous zinc molybdate / zinc phosphate nanoparticles: 10 g of mesoporous zinc molybdate / zinc phosphate nanoparticles were added to 200 mL of ethanol, 1.5 g of silane coupling agent KH550 was added, heated to 45°C, and stirred for 2 h to obtain the modified mesoporous zinc molybdate / zinc phosphate nanoparticles;

[0062] S7. Preparation of a power tower rust-proof and corrosion-resistant coating: 35 g of modified waterborne polyurethane, 8 g of modified epoxy resin emulsion, 1.5 g of N, N-dimethyl ethanol, 0.3 g of dispersant 104BC, 0.15 g of defoamer BYK-024, and 30 mL of water were stirred and mixed uniformly, 3.5 g of modified mesoporous zinc molybdate / zinc phosphate, 2 g of carbon black, and 1.5 g of talc powder were added, and the mixture was ground in a colloidal mill at 11000 r / min for 1 h. Then, 0.7 g of polyurethane RM-8W was added, stirred for 20 min, filtered, and a power tower rust-proof and corrosion-resistant coating was prepared.

[0063] Comparative Example 1

[0064] The difference compared with Example 3 is that no modifier is added in step S2.

[0065] The details are as follows:

[0066] S2. Preparation of modified waterborne polyurethane: 10 g of polytetrahydrofuran diol 2000 was added to 50 mL of acetone, heated to 60°C, and 6 g of toluene diisocyanate was added dropwise. The mixture was stirred and reacted for 1 h. Then, 0.015 g of dibutyltin dilaurate, 1.5 g of dimethylol propionic acid, and 0.3 g of 1,4-butanediol were added, and the reaction was continued for 5 h while stirring. The mixture was cooled to room temperature, 1 g of triethylamine was added, and the mixture was stirred and reacted for 30 min. Then, 30 mL of deionized water was added, emulsified for 25 min, and the acetone was removed under reduced pressure to obtain the waterborne polyurethane.

[0067] Comparative Example 2

[0068] The difference compared with Example 3 is that the modified graphene oxide in step S4 is replaced by an equal amount of graphene oxide.

[0069] The details are as follows:

[0070] S4. Preparation of modified epoxy resin emulsion: 4 g of polyethylene glycol 400 and 5.5 g of epoxy resin DEN-425 were mixed, 0.7 g of boron trifluoride etherate was added, and the mixture was heated to 90°C and stirred and reacted for 4 h to obtain an emulsifier. Then, 3 g of the emulsifier and 70 g of bisphenol A type epoxy resin were added to water, heated to 75°C, and stirred and reacted for 1.5 h. Then, 5.5 g of graphene oxide and 1.5 g of nano silicon dioxide were added, and the mixture was stirred and reacted for 1.5 h. Finally, the mixture was ground in a colloidal mill at 11000 r / min for 2 h to obtain the modified epoxy resin emulsion.

[0071] Comparative Example 3

[0072] The difference compared with Example 3 is that no ammonium phosphate is added in step S5.

[0073] The details are as follows:

[0074] S5. Preparation of mesoporous zinc molybdate nanomaterial: 3.42 g of ammonium molybdate was dissolved in 200 mL of water, 12 g of ethanol and 0.4 g of polyethylene glycol 400 were added, and the mixture was stirred for 30 min, 100 mL of a solution containing 2.74 g of zinc chloride was added dropwise, then 0.15 g of polyvinyl alcohol was added, heated to 60℃, and stirred for 1.5 h, centrifuged, washed, and dried to obtain mesoporous zinc molybdate nanomaterial.

[0075] Comparative Example 4

[0076] The difference compared with Example 3 is that no ammonium molybdate is added in step S5.

[0077] The details are as follows:

[0078] S5. Preparation of mesoporous zinc molybdate nanomaterial: 3.42 g of ammonium molybdate was dissolved in 200 mL of water, 12 g of ethanol and 0.4 g of polyethylene glycol 400 were added, and the mixture was stirred for 30 min, 100 mL of a solution containing 2.74 g of zinc chloride was added dropwise, then 0.15 g of polyvinyl alcohol was added, heated to 60℃, and stirred for 1.5 h, centrifuged, washed, and dried to obtain mesoporous zinc molybdate nanomaterial.

[0079] Comparative Example 5

[0080] The difference compared with Example 3 is that step S6 is not performed.

[0081] The details are as follows:

[0082] S1. Preparation of modifier: 4 g of pinoresinol and 2.5 g of piceid were stirred and mixed for 10 min to obtain a modifier;

[0083] S2. Preparation of modified waterborne polyurethane: 10 g of polytetramethylene glycol 2000 was added to 50 mL of acetone, heated to 60℃, and 6 g of toluene diisocyanate was added dropwise, stirred for 1 h, and then 0.015 g of dibutyltin dilaurate, 1.5 g of dimethylol propionic acid, 0.3 g of 1,4-butanediol, and 3 g of the modifier were added, and the stirring was continued for 5 h, and then the temperature was lowered to room temperature, 1 g of triethylamine was added, and stirred for 30 min, 30 mL of deionized water was added, and emulsified for 25 min, and then the acetone was removed under reduced pressure to obtain a modified waterborne polyurethane;

[0084] S3. Preparation of modified graphene oxide: 1 g of graphene oxide was dissolved in 1000 mL of water, 0.45 g of dopamine hydrochloride and 0.015 g of catalyst were added, heated to 45℃, and stirred for 3 h, and then dried to obtain modified graphene oxide;

[0085] The catalyst is Tris-HCl solution with pH = 9;

[0086] S4. Preparation of modified epoxy resin emulsion: 4 g of polyethylene glycol 400 and 5.5 g of epoxy resin DEN-425 were mixed, 0.7 g of boron trifluoride ether was added, heated to 90°C, stirred for 4 h, and an emulsifier was prepared. 3 g of the emulsifier and 70 g of bisphenol A type epoxy resin were added to water, heated to 75°C, stirred for 1.5 h, then 5.5 g of modified graphene oxide and 1.5 g of nano silicon dioxide were added, stirred for 1.5 h, and 11000 r / min colloidal mill was used for 2 h to prepare the modified epoxy resin emulsion.

[0087] S5. Preparation of mesoporous zinc molybdate / zinc phosphate nanoparticles: 1.96 g of ammonium molybdate and 1.46 g of ammonium phosphate were dissolved in 200 mL of water, 12 g of ethanol and 0.4 g of polyethylene glycol 400 were added, stirred and mixed for 30 min, 100 mL of a solution containing 2.74 g of zinc chloride was added dropwise, then 0.15 g of polyvinyl alcohol was added, heated to 60°C, stirred for 1.5 h, centrifuged, washed, and dried to obtain mesoporous zinc molybdate / zinc phosphate nanoparticles.

[0088] S6. Preparation of power tower rust-proof and corrosion-resistant coating: 35 g of modified waterborne polyurethane, 8 g of modified epoxy resin emulsion, 1.5 g of N,N-dimethyl ethanol, 0.3 g of dispersant 104BC, 0.15 g of defoamer BYK-024 and 30 mL of water were stirred and mixed uniformly, 3.5 g of mesoporous zinc molybdate / zinc phosphate nanoparticles, 2 g of carbon black and 1.5 g of talc were added, 11000 r / min colloidal mill was used for 1 h, 0.7 g of polyurethane RM-8W was added, stirred for 20 min, filtered, and the power tower rust-proof and corrosion-resistant coating was prepared.

[0089] Comparative Example 6

[0090] Compared with Example 3, the difference is that no modified epoxy resin emulsion is added in step S7.

[0091] Specifically as follows:

[0092] S7. Preparation of power tower rust-proof and corrosion-resistant coating: 35 g of modified waterborne polyurethane, 1.5 g of N,N-dimethyl ethanol, 0.3 g of dispersant 104BC, 0.15 g of defoamer BYK-024 and 30 mL of water were stirred and mixed uniformly, 3.5 g of modified mesoporous zinc molybdate / zinc phosphate nanoparticles, 2 g of carbon black and 1.5 g of talc were added, 11000 r / min colloidal mill was used for 1 h, 0.7 g of polyurethane RM-8W was added, stirred for 20 min, filtered, and the power tower rust-proof and corrosion-resistant coating was prepared.

[0093] Comparative Example 7

[0094] Compared with Example 3, the difference is that no modified mesoporous zinc molybdate / zinc phosphate nanoparticles is added in step S7.

[0095] Specifically as follows:

[0096] S7. Preparation of the rust and corrosion resistant coating for power iron tower: 35 g of modified waterborne polyurethane, 8 g of modified epoxy resin emulsion, 1.5 g of N, N-dimethyl ethanol, 0.3 g of dispersant 104BC, 0.15 g of defoamer BYK-024 and 30 mL of water were stirred and mixed uniformly, 2 g of carbon black and 1.5 g of talc were added, and the mixture was subjected to colloid mill at 11000 r / min for 1 h, 0.7 g of polyurethane RM-8W was added, stirred for 20 min, filtered, and the rust and corrosion resistant coating for power iron tower was prepared.

[0097] Test Example 1

[0098] The rust and corrosion resistant coatings for power iron tower prepared in Examples 1-3 and Comparative Examples 1-7 were sprayed on test panels according to the requirements of GB / T1727-2021. The following tests were performed:

[0099] The adhesion test was performed according to the test method for adhesion of coatings (pull-off method) in GB / T5210-2006.

[0100] The pencil hardness test was performed according to GB / T6739-2006.

[0101] The water resistance test was performed according to GB / T1733-1993, with a test temperature of 40℃ and a test time of 24 h.

[0102] The results are shown in Table 1.

[0103] Table 1

[0104] Group Adhesion (grade) Pencil hardness (H) Water resistance Example 1 0 5 No blister, wrinkle, peeling Example 2 0 5 No blister, wrinkle, peeling Example 3 0 5 No blister, wrinkle, peeling Comparative Example 1 1 5 Peeling of coating film, blister Comparative Example 2 1 4 No blister, wrinkle, peeling Comparative Example 3 0 4 No blister, wrinkle, peeling Comparative Example 4 0 4 No blister, wrinkle, peeling Comparative Example 5 1 4 No blister, wrinkle, peeling Comparative Example 6 2 4 No blister, wrinkle, peeling Comparative Example 7 1 3 No blister, wrinkle, peeling

[0105] As can be seen from the above table, the rust and corrosion resistant coatings for power iron tower prepared in Examples 1-3 have high adhesion, high hardness and good water resistance.

[0106] Test Example 2

[0107] The rust and corrosion resistant coatings for power iron tower prepared in Examples 1-3 and Comparative Examples 1-7 were sprayed on test panels according to the requirements of GB / T1727-2021. The following tests were performed:

[0108] The flexibility test was performed according to GB / T1731-2020;

[0109] The impact resistance test was performed according to GB / T1732-2020, with a weight of (1000±1) g, and the film was observed for damage at 4 times magnification. The maximum weight drop height when the film was not damaged was taken as the measurement result.

[0110] The results are shown in Table 2.

[0111] Table 2

[0112] Group Flexibility (mm) Impact resistance (kg-cm) Example 1 0.8 89 Example 2 0.6 92 Example 3 0.5 95 Comparative Example 1 1.1 85 Comparative Example 2 3.6 67 Comparative Example 3 1.9 81 Comparative Example 4 2.1 78 Comparative Example 5 2.7 74 Comparative Example 6 4.7 62 Comparative Example 7 3.3 70

[0113] From the above table, it can be seen that the power tower rust-proof and corrosion-resistant coatings prepared by examples 1-3 have good flexibility, impact resistance and bending performance.

[0114] Test example 3

[0115] The power tower rust-proof and corrosion-resistant coatings prepared by examples 1-3 and comparative examples 1-7 are sprayed on test panels according to the requirements of GB / T1727-2021. The following tests are carried out:

[0116] The neutral salt spray resistance test is carried out on a JD-120 (600L) type salt spray test machine according to the provisions of GB / T1771-2007 “Determination of the Resistance of Paints and Varnishes to Neutral Salt Spray”, and the mass concentration of sodium chloride solution is (50±5) g / L, and the pH is 6.5-7.0.

[0117] The acid resistance is tested according to the immersion method specified in GB / T9274-1988 “Determination of the Resistance of Paints and Varnishes to Liquid Media”, the mass fraction of sulfuric acid is 5%, and the defects are observed after immersion for 24h.

[0118] The organic solvent resistance test is carried out according to the manual rubbing method specified in GB / T23989-2009 “Determination of the Resistance of Coatings to Solvent Wiping”, and the fingers wrapped with absorbent cotton are rubbed back and forth for 25 times, and whether the damage exposes the substrate is observed.

[0119] The results are shown in Table 3.

[0120] Table 3

[0121]

[0122] From the above table, it can be seen that the power tower rust-proof and corrosion-resistant coatings prepared by examples 1-3 have good salt spray resistance, acid resistance and solvent resistance.

[0123] The above is only the preferred embodiment of the present application, and is not intended to limit the present application, any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a rust and corrosion resistant coating for electric power towers, characterized by, Comprising the following steps: S1. Preparation of modifier: uniformly mix piceatannol and resveratrol to obtain a modifier; S2. Preparation of modified waterborne polyurethane: add polytetrahydrofuran diol into acetone, heat, drop isocyanate, stir and react, add catalyst, dimethylol propionic acid, 1,4-butanediol and modifier, continue to stir and react, cool to room temperature, add triethylamine, stir and react, add deionized water, emulsify, remove acetone under reduced pressure, and obtain modified waterborne polyurethane; S3. Preparation of modified graphene oxide: dissolve graphene oxide in water, add dopamine hydrochloride and catalyst, heat and stir to react, and dry to obtain modified graphene oxide; S4. Preparation of modified epoxy resin emulsion: mix polyethylene glycol and multifunctional epoxy resin, add boron trifluoride etherate, heat and stir to react, obtain emulsifier, add emulsifier and epoxy resin into water, heat and stir to react, then add modified graphene oxide and nano silicon dioxide, stir and react, and colloid mill to obtain modified epoxy resin emulsion; S5. Preparation of mesoporous nano zinc molybdate / zinc phosphate: dissolve ammonium molybdate and ammonium phosphate in water, add ethanol and polyethylene glycol, stir and mix uniformly, drop zinc chloride solution, then add polyvinyl alcohol, heat and stir to react, centrifuge, wash, dry, and obtain mesoporous nano zinc molybdate / zinc phosphate; S6. Preparation of modified mesoporous nano zinc molybdate / zinc phosphate: add mesoporous nano zinc molybdate / zinc phosphate into ethanol, add silane coupling agent, heat and stir to react, and obtain modified mesoporous nano zinc molybdate / zinc phosphate; S7. Preparation of power tower rust-proof and corrosion-resistant paint: mix modified waterborne polyurethane, modified epoxy resin emulsion, pH value regulator, dispersant, defoaming agent and water, add modified mesoporous nano zinc molybdate / zinc phosphate, pigment and talc, colloid mill, add thickening agent, stir uniformly, filter, and obtain power tower rust-proof and corrosion-resistant paint.

2. The production method according to claim 1, characterized by, The mass ratio of piceatannol and resveratrol in step S1 is 3-5:2-3.

3. The preparation method according to claim 1, characterized in that, The mass ratio of polytetrahydrofuran diol, isocyanate, catalyst, dimethylol propionic acid, 1,4-butanediol, modifier and triethylamine in step S2 is 10:5-7:0.01-0.02:1-2:0.2-0.4:2-4:0.5-1.5, the heating temperature is 55-65℃, the isocyanate is at least one selected from isophorone diisocyanate, toluene diisocyanate, diphenyl methane diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, the catalyst is dibutyl tin dilaurate or stannous octoate, and the emulsification time is 20-30min.

4. The method of claim 1, wherein, The mass ratio of graphene oxide, dopamine hydrochloride and catalyst in step S3 is 10:3-6:0.1-0.2, the heating and stirring temperature is 40-50℃, and the time is 2-4h, and the catalyst is Tris-HCl solution with pH=8.5-9.

5.

5. The preparation method according to claim 1, characterized in that, The mass ratio of the polyethylene glycol, the multifunctional epoxy resin, and the boron trifluoride ether in step S4 is 3-5:4-7:0.5-1, the multifunctional epoxy resin is epoxy resin DEN-425, the mass ratio of the emulsifier, the epoxy resin, the modified graphene oxide, and the nano-silica is 2-4:60-80:4-7:1-2, the rotating speed of the colloid mill is 10000-12000r / min, the time is 1-3h, and the epoxy resin is a bisphenol A or bisphenol F type epoxy resin.

6. The method of claim 1, wherein, The mass ratio of the ammonium molybdate, the ammonium phosphate, the ethanol, the polyethylene glycol, the zinc chloride, and the polyvinyl alcohol in step S5 is 1.9-2.0:1.4-1.5:10-15:0.3-0.5:2.6-2.8:0.1-0.2, the temperature of the heating and stirring reaction is 55-65℃, and the time is 1-2h.

7. The preparation method according to claim 1, characterized in that, The mass ratio of the mesoporous nano-zinc molybdate / zinc phosphate and the silane coupling agent in step S6 is 10:1-2, the silane coupling agent is at least one selected from KH550, KH692, and KH702, the temperature of the heating and stirring reaction is 40-50℃, and the time is 1-3h.

8. The method of claim 1, wherein, The mass ratio of the modified waterborne polyurethane, the modified epoxy resin emulsion, the pH value regulator, the dispersant, the defoaming agent, water, the modified mesoporous nano-zinc molybdate / zinc phosphate, the pigment, the talc powder, and the thickening agent in step S7 is 30-40:7-10:1-2:0.2-0.4:0.1-0.2:20-40:3-4:1-3:1-2:0.5-1, the dispersant is 104BC, the defoaming agent is BYK-024, the pigment is carbon black, and the thickening agent is polyurethane RM-8W.

9. A rust and corrosion resistant coating for electric power towers, prepared by the method of any one of claims 1-8.

Images