CN115873478A - High-solid polyaniline epoxy anticorrosive primer and preparation method thereof - Google Patents
High-solid polyaniline epoxy anticorrosive primer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-solid polyaniline epoxy anticorrosive primer and a preparation method thereof, and relates to the technical field of metal substrate protective coatings. The invention discloses a polyaniline epoxy anticorrosive primer which comprises a component A and a component B, wherein the component A comprises the following components in percentage by weight: 18-25% of epoxy resin, 3-5% of polyfunctional epoxy active diluent, 2-6% of oligomer, 1-10% of doped polyaniline, 5-9% of organic solvent, 50-70% of extender pigment and 2-4% of auxiliary agent; the component B comprises the following components in percentage by weight: 85-90% of epoxy curing agent and 10-15% of organic solvent; and the component A and the component B are mixed according to the weight ratio of 6:1, mixing uniformly to obtain the product. The high-solid polyaniline epoxy anticorrosive primer provided by the invention can be sprayed once to form a thick film so as to be adhered to steel, has excellent adhesive force, heat resistance, impact resistance and salt mist resistance, and has a long-acting anticorrosive effect and outstanding anti-sagging performance.
Description
Technical Field
The invention belongs to the technical field of metal substrate protective coatings, and particularly relates to a high-solid polyaniline epoxy anticorrosive primer suitable for the heavy-duty anticorrosive field and a preparation method thereof, which can be used for steel protection instead of epoxy zinc-rich primer.
Background
The steel is easy to be oxidized and corroded in humid air, so that the steel structure bridge is corroded to generate corrosion, and the service life and the attractiveness of the bridge are influenced. When the anti-corrosion maintenance is carried out on the bridge steel structure, the corrosion environment of the area where the steel structure bridge is located must be known, and then the anti-corrosion maintenance scheme is provided according to the relevant standard of the anti-corrosion coating of the bridge steel structure.
In the process of development and utilization of marine resources, the corrosion resistance of steel is not only influenced by the chemical composition of the steel, the surface state and other material factors, but also controlled by marine environmental conditions. The marine environment of the same area can be divided into an atmospheric area, a splash area, a tidal range area, a full immersion area and a slurry area in the vertical direction. In addition to the different effects of these areas on steel corrosion, the marine environment in the same area also contains many factors, such as salinity, pH, temperature, dissolved gas flow rate, microorganisms and pollution, which sometimes interact and promote each other, resulting in a very complex process of steel corrosion from the sea. Seawater is a complex electrolyte system, and the seawater environmental factors (such as temperature, oxygen content and the like) change greatly along with the change of conditions of sea areas, high stratification, seasons and the like, so that the corrosion speed of metal changes along with the environmental factors.
The heavy-duty anticorrosive paint is mainly used for corrosion protection of steel products, and is widely applied to the industrial fields of ocean engineering, petrochemical industry, railways, ships, bridges, engineering machinery, containers and the like. The existing heavy-duty anticorrosive paint in the market is mainly represented by zinc-containing paint such as epoxy zinc-rich paint, and the anticorrosion principle is to perform anticorrosion protection through metal zinc electrochemical reaction, namely, metal zinc replaces iron to be corroded and consumed, so the strength of the corrosion protection capability of the paint is determined by the zinc content. The anticorrosion principle of the zinc-containing anticorrosive paint mainly depends on adding metal zinc powder, and the zinc powder is used as an antirust agent. However, metal zinc belongs to toxic heavy metals, and heavy metal pollution is easily caused by using zinc powder on a large scale. And the continuous and stable supply of zinc powder is also a concern, and according to the data of the American geological survey bureau, the global zinc storage is 2.5 hundred million tons, the annual production amount is 1300 ten thousand tons, and the static production period of the global zinc resource is 19 years, so that the updating of heavy-duty anticorrosion products is imminent, and the zinc anticorrosion period is about to end in the near future along with the exhaustion of zinc energy.
In an organic anticorrosive paint system, the epoxy resin paint is the main force of heavy anticorrosive paint, mainly because the epoxy resin paint has strong adhesive force and better comprehensive anticorrosive performance, but has poorer acid resistance and higher temperature resistance. For epoxy resin coating, the curing agent has a great influence on the performance of the epoxy resin coating, and if the solubility parameters of the epoxy resin component and the curing agent are well matched, uniform mixing and curing can be achieved, so that the optimal curing effect is achieved; the solubility parameters with larger or smaller difference can affect the compatibility and the dispersibility of each component, thereby leading the combination property to be poorer.
The polyaniline anticorrosive paint is an environment-friendly efficient anticorrosive paint which is developed in recent years, has an anticorrosive mechanism which is not possessed by a conventional anticorrosive paint, can passivate the surface of protected metal, has a shielding effect different from that of the conventional anticorrosive paint, and is relatively more effective than the current most effective metal anticorrosive pigments, namely heavy metals such as chromium, lead or zinc which seriously pollute the environment. However, the rigidity of the molecular chain of polyaniline is very high, the processing is difficult, the dispersibility of polyaniline in the conventional coating resin is poor, the cost is high, and the process of the polyaniline can be greatly limited. Chinese patent CN103834265A discloses a polyaniline anticorrosive coating, wherein phosphoric acid-phosphate ester dopant, eigenstate polyaniline and water are mixed and then added into the coating to prepare the aqueous polyaniline anticorrosive coating, which has excellent anticorrosive performance, but the doped polyaniline prepared by the patent is only suitable for aqueous coating systems and cannot be used in solvent-based coating systems, and the adhesion between the doped polyaniline and organic silicon antifouling finish paint is poor (an intermediate connecting layer is required to be arranged between the finish paint and a primer paint), and the temperature resistance is general.
Disclosure of Invention
The invention aims to provide a high-solid polyaniline epoxy anticorrosive primer which can be sprayed once to form a thick film so as to be adhered to steel, has excellent adhesive force, temperature resistance, impact resistance and salt mist resistance, and has a long-acting anticorrosive effect and outstanding sagging resistance.
In order to achieve the purpose of the invention, the invention provides a high-solid polyaniline epoxy anticorrosive primer, which comprises a component A and a component B, wherein the component A comprises the following components in percentage by weight:
18 to 25 percent of epoxy resin;
3-5% of polyfunctional epoxy reactive diluent;
2 to 6 percent of oligomer;
doped polyaniline 1-10%;
5 to 9 percent of organic solvent;
50-70% of extender pigment;
1 to 4 percent of auxiliary agent;
the component B comprises the following components in percentage by weight:
85 to 90 percent of epoxy curing agent;
10 to 15 percent of organic solvent.
Furthermore, the epoxy resin is bisphenol A type liquid epoxy resin, the epoxy equivalent EEW is 180-190 g/eq, and the viscosity is 8000-15000 cps.
Furthermore, the multifunctional epoxy active diluent consists of 1-2 wt% of monofunctional cardanol active diluent and 2-3.5 wt% of difunctional cardanol active diluent. The cardanol active diluent with the single functional group and the bifunctional group is used for matching, so that the adhesive force and the corrosion prevention effect of the product are improved.
Further, the oligomer is petroleum resin with molecular weight of 500-2000.
Further, the doped polyaniline is prepared by mixing phosphoric acid, isopropyl orthosilicate, eigenstate polyaniline and N-methylpyrrolidone;
the preparation method of the doped polyaniline comprises the following steps:
adding isopropyl n-silicate into 5-10 wt% phosphoric acid solution, and mixing for 30min to obtain a mixed dopant; then mixing the mixed dopant, the eigenstate polyaniline and the N-methyl pyrrolidone, stirring and reacting for 3-5 h, and then drying in a drying oven at 100 ℃ for 1-2 h to prepare the doped polyaniline.
Further, the molar ratio of the isopropyl n-silicate to the phosphoric acid in the phosphoric acid solution is 1: (0.5-0.6), the molar ratio of the isopropyl N-silicate to the intrinsic polyaniline to the N-methylpyrrolidone is (0.3-0.5): 1:1.
further, the organic solvent is any one or a mixed solvent of xylene and n-butanol;
the extender pigment is one or more of silica micropowder, potassium feldspar powder or talcum powder;
the auxiliary agent is a combination of any two or more of a defoaming agent, a dispersing agent, a wetting agent, a silane coupling agent, a flatting agent or an adhesion promoter.
Further, the epoxy curing agent is any one of phenolic aldehyde amine epoxy curing agent or hydroxy silicone oil modified phenolic aldehyde amine epoxy curing agent.
Further, the preparation method of the hydroxyl silicone oil modified phenolic aldehyde amine epoxy curing agent comprises the following steps:
adding hydroxyl silicone oil into 1mol/L NaOH solution, stirring uniformly, then adding phenolic aldehyde amine epoxy curing agent, and stirring and reacting for 1-2 h at normal temperature to obtain the epoxy resin composition;
the mass ratio of the hydroxyl silicone oil to the NaOH solution is 1:4, the mass ratio of the hydroxyl silicone oil to the phenolic aldehyde amine epoxy curing agent is (0.05-0.1): 1.
the invention also provides a preparation method of the high-solid polyaniline epoxy anticorrosive primer, which comprises the following steps:
(1) Putting epoxy resin, polyfunctional epoxy active diluent, oligomer, doped polyaniline, organic solvent, extender pigment, defoaming agent, dispersing agent and wetting agent into a sand mill, grinding until the particle size is below 50 mu m, then adding silane coupling agent for size mixing, and fully dispersing for 30min under the action of a high-speed dispersion machine to prepare a component A;
(2) Fully mixing the epoxy curing agent and the organic solvent for 10-30 min to prepare a component B;
(3) The component A and the component B are mixed according to the weight ratio of 6:1, uniformly mixing, and spraying air on the bottom plate.
The invention achieves the following beneficial effects:
1. the invention adopts phosphoric acid, silicate ester, eigenstate polyaniline and N-methyl pyrrolidone to mix according to a certain preparation process to prepare doped polyaniline, the doped polyaniline plays a role of a catalyst in a paint film of the invention, so that the polyaniline and iron react to generate a compact oxide film, and the polyaniline is repeatedly reduced and oxidized, thereby achieving the purpose of long-acting corrosion prevention; the addition of silicate ester can not only promote the improvement of anticorrosion efficiency, but also improve the water resistance and high and low temperature stability of the invention.
2. According to the invention, the phenolic aldehyde amine epoxy curing agent is adopted, and contains phenolic hydroxyl, amine active hydrogen and a phenolic aldehyde skeleton structure, so that the curing reaction speed is improved, a highly-meshed cross-linked structure is easily formed with the components such as epoxy resin, doped polyaniline and the like in the application, and the excellent corrosion resistance of the epoxy resin and the polyaniline can be maintained, so that the product has excellent corrosion resistance, the long-acting corrosion prevention effect is achieved, and the product can be applied to an anticorrosive coating in the marine field; according to the invention, the phenolic aldehyde amine epoxy curing agent is modified by using the hydrogenated silicone oil, and the silicon-containing low-viscosity hydroxyl active molecules are introduced into the phenolic aldehyde amine curing agent, so that the curing time is accelerated, the components such as epoxy resin and doped polyaniline are easily cured and connected, and the phenolic aldehyde amine curing agent, the organic silicon finish paint and the metal substrate have good cohesive force and high adhesive strength through the formation of bonding among chemical bonds such as amino groups and epoxy groups, so that the corrosion resistance, the high and low temperature resistance, the weather resistance and the water resistance of the product are improved, and the corrosion resistance life of the product is prolonged.
3. The hydrogenated silicone oil can react with phenolic hydroxyl, primary amino and the like in the phenolic aldehyde amine epoxy curing agent under an alkaline condition, so that the curing speed is improved on the basis of improving the activity of the curing agent, the cured silicone oil can be rapidly cured in a low-temperature and humid environment, and the high-temperature and low-temperature stability, the waterproof and anticorrosive performance of the product can be improved; the phenolic aldehyde amine epoxy curing agent is modified under a proper amount of alkaline conditions, so that the obtained modified curing agent has better activity and better curing performance, and if the amount of alkaline solution is less, namely the alkalinity is lower, the curing activity is influenced; if the alkalinity is too strong, the corrosion resistance of the present invention is affected.
4. The primer disclosed by the invention can achieve a long-term protection effect on steel by about 80 microns, is high in corrosion resistance efficiency and good in coating effect, can replace the traditional zinc-rich coating, does not contain heavy metal, is low in VOC (volatile organic compounds), and belongs to an environment-friendly product.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
The invention provides a high-solid polyaniline epoxy anticorrosive primer, which comprises a component A and a component B, wherein the component A comprises:
18 to 25 percent of epoxy resin;
3-5% of polyfunctional epoxy reactive diluent;
2 to 6 percent of oligomer;
doped polyaniline 1-10%;
5 to 9 percent of organic solvent;
50 to 70 percent of extender pigment;
1 to 4 percent of auxiliary agent;
the component B comprises the following components in percentage by weight:
85 to 90 percent of epoxy curing agent;
10 to 15 percent of organic solvent.
The high-solid polyaniline epoxy primer provided by the invention is mainly used for protecting steel from rusting, the main performance of the primer depends on the ratio of epoxy resin to doped polyaniline, and the epoxy resin and doped polyaniline which are mixed according to the ratio provided by the invention can achieve the effect of long-term protection on the steel by about 80 mu m, and can also be applied to the field of seawater corrosion prevention.
Preferably, the epoxy resin is bisphenol A type liquid epoxy resin, the epoxy equivalent EEW is 180-190 g/eq, the viscosity is 8000-15000 cps, the content is 18-23 wt%, and the more preferable content is 18-20 wt%. The epoxy resin is selected from south Asia 128, is mainly used as a film forming substance, is doped with polyaniline and cardanol active diluent and is used as an auxiliary component, so that the primer disclosed by the invention can be better adhered to a substrate, has excellent adhesive force and is not easy to fall off.
Preferably, the multifunctional epoxy active diluent consists of 1-2 wt% of monofunctional cardanol active diluent and 2-3.5 wt% of difunctional cardanol active diluent, wherein the weight percentage of the component A is calculated. The content of the monofunctional cardanol reactive diluent is preferably 1.2 to 1.8wt%, more preferably 1.5 to 1.7wt%. The monofunctional cardanol active diluent disclosed by the invention is WSCM-5110 in model, is low in viscosity, can improve toughness and water resistance, and is used for a high-solid or solvent-free system; the bifunctional cardanol reactive diluent is PRO602 with biotin resistance, and can improve the cohesion and crosslinking density of a paint film, so that the cohesion strength, water resistance and chemical resistance of the paint film are improved. The selected monofunctional group cardanol active diluent and bifunctional group cardanol active diluent are combined, the cardanol active diluent has 100% of solid, the viscosity is low, and the adhesion and the anticorrosion effect of the product are improved.
Preferably, the oligomer is a petroleum resin having a molecular weight of 500 to 2000. The oligomer selected by the invention is Yuemization C9 petroleum resin, and the oligomer has 100 percent of solid content and lower viscosity.
Preferably, the doped polyaniline is prepared by mixing phosphoric acid, isopropyl orthosilicate, intrinsic polyaniline and N-methylpyrrolidone;
the preparation method of the doped polyaniline comprises the following steps:
adding isopropyl n-silicate into 5-10 wt% phosphoric acid solution, and mixing for 30min to obtain a mixed dopant; and then mixing the mixed dopant, the eigenstate polyaniline and the N-methylpyrrolidone, stirring for reaction for 3-5 hours, and then drying in an oven at 100 ℃ for 1-2 hours to obtain the doped polyaniline.
The content of the self-made doped polyaniline is preferably 1 to 6wt%, and more preferably 2 to 5wt%. The self-made doped polyaniline is prepared by doping eigenstate polyaniline with phosphoric acid-silicate ester, so that the polyaniline can be dissolved in N-methyl pyrrolidone, the solubility of the polyaniline in a solvent epoxy resin coating can be improved, the dispersion stability of the polyaniline in the solvent epoxy resin coating is improved, and the polyaniline can achieve high-efficiency anticorrosion effect in the product; in addition, the silicate ester is doped, so that the corrosion prevention efficiency can be improved, and the water resistance and the high and low temperature stability of the invention can be improved.
Preferably, the molar ratio of isopropyl n-silicate to phosphoric acid in the phosphoric acid solution is 1: (0.5-0.6), the molar ratio of the isopropyl N-silicate to the intrinsic polyaniline to the N-methylpyrrolidone is (0.3-0.5): 1:1.
preferably, the organic solvent in the component A is any one or a mixed solvent of xylene and n-butanol, and the xylene and the n-butanol in the invention are selected from chemical industry of Huayang.
Preferably, the organic solvent in component B is selected from xylene in Wasun chemical industry.
Preferably, the extender pigment is one or more of silica micropowder, potassium feldspar powder or talcum powder, and the sagging resistance and the wear resistance of the invention can be obviously improved.
Preferably, the auxiliary agent is a combination of any two or more of a defoaming agent, a dispersing agent, a wetting agent, a silane coupling agent, a leveling agent or an adhesion promoter. The content of the auxiliary agent is preferably 2 to 3 weight percent, more preferably 2.5 to 2.8 weight percent, wherein the content of the dispersing agent is 0.8 to 1.2 weight percent, and the content of the leveling agent is 1.3 to 2 percent.
Preferably, the epoxy curing agent is any one of a phenolic aldehyde amine epoxy curing agent or a hydroxy silicone oil-modified phenolic aldehyde amine epoxy curing agent. The phenolic amine epoxy curing agent used in the present invention was selected from 1101 in air chemistry.
Preferably, the preparation method of the hydroxyl silicone oil modified phenolic aldehyde amine epoxy curing agent comprises the following steps:
adding hydroxyl silicone oil into 1mol/L NaOH solution, stirring uniformly, then adding phenolic aldehyde amine epoxy curing agent, and stirring and reacting for 1-2 h at normal temperature to obtain the epoxy resin composition;
the mass ratio of the hydroxyl silicone oil to the NaOH solution is 1:4, the mass ratio of the hydroxyl silicone oil to the phenolic aldehyde amine epoxy curing agent is (0.05-0.1): 1.
the invention also provides a preparation method of the high-solid polyaniline epoxy anticorrosive primer, which comprises the following steps:
(1) Putting epoxy resin, polyfunctional epoxy active diluent, oligomer, doped polyaniline, organic solvent, extender pigment, defoaming agent, dispersing agent and wetting agent into a sand mill, grinding until the particle size is below 50 mu m, then adding silane coupling agent for size mixing, and fully dispersing for 30min under the action of a high-speed dispersion machine to prepare a component A;
(2) Fully mixing the epoxy curing agent and the organic solvent for 10-30 min to prepare a component B;
(3) The component A and the component B are mixed according to the weight ratio of 6:1, uniformly mixing, and spraying air on the bottom plate.
The high-solid polyaniline epoxy anti-corrosive primer of the present invention is further described with reference to the following specific examples.
The block modified fatty acid polymer dispersant in the embodiment of the invention is selected from BYK104 of Bick, germany; the polyacrylate wetting and leveling agent is selected from EFKA3777; the acetylenic diol wetting agent is selected from Surfynol 104; the silicone antifoaming agent is selected from the group consisting of modesty 6800.
Example 1
The preparation method of the high-solid polyaniline epoxy anticorrosive primer comprises the following steps:
component A: taking 18wt% of 128 epoxy resin, 1.6wt% of 5110 cardanol epoxy active diluent, 3.4wt% of PRO602 cardanol epoxy active diluent, 6wt% of C9 oligomer, 2wt% of doped polyaniline, 8wt% of xylene organic solvent, 50 wt% of silicon micropowder and 7wt% of talcum powder, adding 0.2 wt% of assistant polysiloxane defoaming agent, 1.2wt% of block modified fatty acid high-molecular dispersant and 1.5wt% of polyacrylate wetting and leveling agent, passing through a 60L bedroom sand mill, enabling the fineness to be below 50 micrometers, adding 1wt% of silane coupling agent in a size mixing stage, and fully dispersing for 30 minutes.
The preparation method of the doped polyaniline comprises the following steps: adding isopropyl n-silicate into 8wt% phosphoric acid solution, and mixing for 30min to obtain mixed dopant; and then mixing the mixed dopant, the eigenstate polyaniline and the N-methylpyrrolidone, stirring for reacting for 4 hours, and then drying in an oven at 100 ℃ for 2 hours to obtain the doped polyaniline. Wherein the molar ratio of the isopropyl n-silicate to the phosphoric acid in the phosphoric acid solution is 2:1, the molar ratio of isopropyl N-silicate to intrinsic polyaniline to N-methylpyrrolidone is 1:2:2. it should be noted that the doped polyaniline used in the examples of the present invention has the same composition, content, and preparation method as the doped polyaniline in example 1, i.e., the doped polyaniline is the same.
Preparing a component B: mixing 85wt% of phenolic aldehyde amine epoxy curing agent and 15wt% of xylene organic solvent for 30 minutes, and packaging. Then, the component A and the component B are mixed according to the weight ratio of 6:1, uniformly mixing to obtain the polyaniline epoxy anticorrosive primer with high solid content.
The high-solid polyaniline epoxy anticorrosive primer prepared in example 1 is applied to the surface of a cold-rolled steel sheet, and the application method comprises the following steps: the cold-rolled steel plate is subjected to 240-mesh sand paper grinding or sand blasting treatment, dust removal is carried out, then air spraying is carried out, the film thickness is about 80 microns, and the performance detection results are shown in the following table 1. The performance of the high-solid polyaniline epoxy anticorrosive primer of example 1 was compared with that of an epoxy zinc-rich primer (a brand known from international countries) and that of a cold spray zinc paint (a brand known from domestic countries), and the detection results are shown in table 1 below.
Table 1 results of performance testing of example 1
Example 2
The preparation method of the high-solid polyaniline epoxy anticorrosive primer comprises the following steps:
and (2) component A: taking 18wt% of 128 epoxy resin, 1.6wt% of 5110 cardanol epoxy active diluent, 3.4wt% of PRO602 cardanol epoxy active diluent, 5wt% of C9 oligomer, 3wt% of doped polyaniline, 8wt% of xylene organic solvent, 50 wt% of silicon micropowder and 6wt% of talcum powder, adding 0.2 wt% of assistant polysiloxane defoaming agent, 1.3wt% of block modified fatty acid high-molecular dispersant and 2wt% of acetylene glycol wetting agent, passing through a 60L bedroom sand mill, enabling the fineness to be below 50 micrometers, adding 2wt% of silane coupling agent in a size mixing stage, and fully dispersing for 30 minutes.
Preparing a component B: mixing 85wt% of phenolic aldehyde amine epoxy curing agent and 15wt% of xylene organic solvent for 30 minutes, and packaging. Then, the component A and the component B are mixed according to the weight ratio of 6:1, uniformly mixing to obtain the polyaniline epoxy anticorrosive primer with high solid content.
Example 3
The preparation method of the high-solid polyaniline epoxy anticorrosive primer comprises the following steps:
and (2) component A: taking 18wt% of 128 epoxy resin, 1.6wt% of 5110 cardanol epoxy active diluent, 3.4wt% of PRO602 cardanol epoxy active diluent, 5wt% of C9 oligomer, 4wt% of doped polyaniline, 8wt% of xylene organic solvent, 50 wt% of silicon micropowder and 5wt% of talcum powder, adding 0.2 wt% of assistant polysiloxane defoaming agent, 1.3wt% of block modified fatty acid high-molecular dispersant and 2wt% of acetylene glycol wetting agent, passing through a 60L bedroom sand mill, enabling the fineness to be below 50 micrometers, adding 2wt% of silane coupling agent in a size mixing stage, and fully dispersing for 30 minutes.
Preparing a component B: mixing 85wt% of phenolic aldehyde amine epoxy curing agent and 15wt% of xylene organic solvent for 30 minutes, and packaging. Then, the component A and the component B are mixed according to the weight ratio of 6:1, uniformly mixing to obtain the polyaniline epoxy anticorrosive primer with high solid content.
Example 4
The preparation method of the high-solid polyaniline epoxy anticorrosive primer in this example 4 is the same as that in example 3, with specific reference to example 3, except that the epoxy curing agent in this example 4 is a hydroxy silicone oil-modified phenol aldehyde amine epoxy curing agent. The preparation method of the hydroxyl silicone oil modified phenolic aldehyde amine epoxy curing agent comprises the following steps: adding 1kg of hydroxyl silicone oil into 4kg of 1mol/L NaOH solution, uniformly stirring, then adding 10kg of phenolic aldehyde amine epoxy curing agent, and stirring and reacting for 2 hours at normal temperature.
The high-solid polyaniline epoxy anticorrosive primer prepared in examples 1-4 is applied to the surface of a cold-rolled steel sheet, and the application method comprises the following steps: the cold-rolled steel plate is subjected to 240-mesh sand paper grinding or sand blasting treatment, dust is removed, then air spraying is carried out, the film thickness is about 80 micrometers, and the performance detection results are shown in the following table 2. The performances of the high-solid polyaniline epoxy anticorrosive primer of the invention are compared with epoxy zinc-rich primer (the international brand is selected) and cold spray zinc paint (the domestic brand is selected), and the detection results are shown in the following table 2.
Table 2 performance test results of high-solid polyaniline epoxy anticorrosive primer
As can be seen from the salt spray test of the detection results in the table 2 above, the addition amount of the doped polyaniline has a remarkable effect on the corrosion resistance of the coating, and compared with the traditional zinc-rich coating, the corrosion resistance has an obvious advantage; meanwhile, the coating is obviously superior to the traditional coating in sag resistance, and has great advantages in construction. In addition, the phenolic aldehyde amine epoxy curing agent modified by the hydroxyl silicone oil is applied to the invention, so that the heat resistance of the product is obviously improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. The high-solid polyaniline epoxy anticorrosive primer is characterized by comprising a component A and a component B, wherein the component A comprises the following components in percentage by weight:
18 to 25 percent of epoxy resin;
3-5% of polyfunctional epoxy reactive diluent;
2 to 6 percent of oligomer;
doped polyaniline 1-10%;
5 to 9 percent of organic solvent;
50-70% of extender pigment;
1 to 4 percent of auxiliary agent;
the component B comprises the following components in percentage by weight:
85 to 90 percent of epoxy curing agent;
10 to 15 percent of organic solvent.
2. The high-solid polyaniline epoxy anticorrosion primer as claimed in claim 1, wherein the epoxy resin is bisphenol a type liquid epoxy resin, the epoxy equivalent EEW is 180-190 g/eq, and the viscosity is 8000-15000 cps.
3. The high-solid polyaniline epoxy anticorrosive primer according to claim 1, wherein the multifunctional epoxy reactive diluent consists of 1-2 wt% of monofunctional cardanol reactive diluent and 2-3.5 wt% of difunctional cardanol reactive diluent.
4. The high-solid polyaniline epoxy anticorrosion primer as claimed in claim 1, wherein the oligomer is a petroleum resin with a molecular weight of 500-2000.
5. The high-solid polyaniline epoxy anticorrosive primer as claimed in claim 1, wherein the doped polyaniline is prepared by mixing phosphoric acid, isopropyl orthosilicate, intrinsic polyaniline and N-methylpyrrolidone;
the preparation method of the doped polyaniline comprises the following steps:
adding isopropyl n-silicate into 5-10 wt% phosphoric acid solution, and mixing for 30min to obtain a mixed dopant; and then mixing the mixed dopant, the eigenstate polyaniline and the N-methylpyrrolidone, stirring for reaction for 3-5 hours, and then drying in an oven at 100 ℃ for 1-2 hours to obtain the doped polyaniline.
6. The high-solid polyaniline epoxy anticorrosive primer according to claim 5, wherein the molar ratio of isopropyl n-silicate to phosphoric acid in phosphoric acid solution is 1: (0.5-0.6), the molar ratio of the isopropyl N-silicate to the intrinsic polyaniline to the N-methylpyrrolidone is (0.3-0.5): 1:1.
7. the high-solid polyaniline epoxy anticorrosion primer as claimed in claim 1, wherein the organic solvent is a mixed solvent of xylene and n-butanol;
the extender pigment is one or more of silica micropowder, potassium feldspar powder or talcum powder;
the auxiliary agent is a combination of any two or more of a defoaming agent, a dispersing agent, a wetting agent, a silane coupling agent, a flatting agent or an adhesion promoter.
8. The high-solid polyaniline epoxy anticorrosive primer according to claim 1, wherein the epoxy curing agent is any one of a phenolic aldehyde amine epoxy curing agent or a hydroxy silicone oil-modified phenolic aldehyde amine epoxy curing agent.
9. The high-solid polyaniline epoxy anticorrosive primer as claimed in claim 8, wherein the preparation method of the hydroxyl silicone oil modified phenolic aldehyde amine epoxy curing agent comprises the following steps:
adding hydroxyl silicone oil into a 1mol/L NaOH solution, uniformly stirring, then adding a phenolic aldehyde amine epoxy curing agent, and stirring and reacting for 1-2 hours at normal temperature to obtain the epoxy resin composition;
the mass ratio of the hydroxyl silicone oil to the NaOH solution is 1:4, the mass ratio of the hydroxyl silicone oil to the phenolic aldehyde amine epoxy curing agent is (0.05-0.1): 1.
10. the preparation method of the high-solid polyaniline epoxy anticorrosive primer as claimed in any one of claims 1 to 9, which comprises the following steps:
(1) Putting epoxy resin, epoxy active diluent, oligomer, doped polyaniline, organic solvent, extender pigment, defoaming agent, dispersing agent and wetting agent into a sand mill, grinding until the particle size is less than 50 mu m, then adding silane coupling agent for size mixing, and fully dispersing for 30min under the action of a high-speed dispersion machine to obtain a component A;
(2) Fully mixing the epoxy curing agent and the organic solvent for 10-30 min to prepare a component B;
(3) The component A and the component B are mixed according to the weight ratio of 6:1, uniformly mixing, and spraying air on the bottom plate.
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| CN202211738431.9A CN115873478A (en) | 2022-12-31 | 2022-12-31 | High-solid polyaniline epoxy anticorrosive primer and preparation method thereof |
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Cited By (1)
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| CN116716015A (en) * | 2023-06-27 | 2023-09-08 | 上海青济新材料发展有限公司 | Container, epoxy anticorrosive paint and preparation method thereof |
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