CN107236437B - Water-based anticorrosive paint and preparation method thereof - Google Patents

Abstract

The invention relates to the field of coatings, and particularly discloses a water-based anticorrosive coating and a preparation method thereof. The water-based anticorrosive paint comprises a component A and a component B; the component A comprises the following components in parts by mass: 15-25 parts of water-based isocyanate curing agent, 15-55 parts of zinc powder, 1-5 parts of defoaming agent, 1-5 parts of wetting dispersant, 0.9-2 parts of anti-settling thixotropic agent, 0.1-5 parts of conductive polymer/fullerene composite material, 0.5-1 part of flash rust inhibitor, 0.5-1 part of flatting agent, 1-3.5 parts of adhesion promoter and 5-15 parts of antirust pigment; the component B comprises the following components in parts by mass: 5-13 parts of methyl methacrylate, 15-25 parts of butyl acrylate, 7-16 parts of styrene, 15-30 parts of epoxy resin, 1-6 parts of methacrylic acid, 1-5 parts of acrylamide, 1.5-2 parts of hydroxyethyl acrylate, 0.5-5 parts of emulsifier, 0.5-5 parts of initiator, 80-130 parts of deionized water and 0.1-1 part of ammonia water, wherein the prepared component A and the component B are stirred and mixed according to the mass ratio of 8-16:1, and the coating has the advantages of strong shielding property, excellent corrosion resistance, environmental protection, good flexibility and strong adhesive force.

Description

A kind of water-based anti-corrosion coating and preparation method thereof

technical field

The invention belongs to the field of coatings, and in particular relates to a water-based anti-corrosion coating and a preparation method thereof.

Background technique

Corrosion is a phenomenon in which a metal material is destroyed by chemical or electrochemical action with the surrounding medium to become a metal compound. Corrosion will cause huge losses every year in the world, especially for my country, which temporarily ranks first in the world in terms of steel production. About 6% of the total value, so the anti-corrosion treatment is particularly important.

Zinc-rich paint, which utilizes the anti-corrosion mechanism of zinc's lower electrode potential to play a cathodic protection effect on iron, has become an excellent anti-corrosion paint. In the traditional solvent-based zinc-rich primer, in order to ensure good cathodic protection, the standard HG/T3668-2009 stipulates that the metal zinc content in the non-volatile matter is not less than 80%, but the zinc content is too high to cause the toughness of the zinc-rich coating. , The adhesion is reduced, thus affecting the anti-corrosion effect. At the same time, the zinc powder will be heated to produce a large amount of zinc oxide mist during welding, which will endanger the health of operators and cause environmental pollution.

At present, sheet-like nanomaterials such as nano-montmorillonite, graphene, etc. are generally used to replace part of zinc powder. Chinese patent CN105086758 A discloses a graphene two-component anti-corrosion coating, in which graphene plays a role of shielding and protection. The flake nano-shielding material can effectively exert the shielding ability against corrosion factors (O ₂ and H ₂ O) only when it is parallel to the protective matrix, however, the orientation of nano-sized flake graphene in the coating is random, and only partial Graphene plays a shielding role, and the utilization rate of graphene is low. In anti-corrosion coatings using sheet-shaped shielding materials, there is a common problem that the shielding materials are randomly arranged and the utilization efficiency is low.

SUMMARY OF THE INVENTION

Aiming at the problems of low toughness and adhesion of the existing zinc-rich coatings, environmental pollution and low utilization efficiency of shielding materials in anti-corrosion coatings, a water-based anti-corrosion coating and a preparation method thereof are provided. It has the advantages of strong shielding, excellent anti-corrosion performance, green environmental protection, good flexibility, strong adhesion, and simple process.

In order to solve the above-mentioned technical problems, the technical scheme adopted by the present invention is:

A water-based anti-corrosion coating, including component A and component B;

The component A includes the following components in parts by mass:

15-25 parts of water-based isocyanate curing agent,

15-55 parts of zinc powder,

1-5 parts of defoamer,

Wetting and dispersing agent 1-5 parts,

Anti-settling thixotropic agent 0.9-2 parts,

0.1-5 parts of conductive polymer/ fullerene composite material, wherein the mass ratio of conductive polymer material to fullerene is 1:5-95,

Anti-flash rust agent 0.5-1 part,

Leveling agent 0.5-1 part,

Adhesion promoter 1-3.5 parts,

5-15 copies of anti-rust pigment;

The component B includes the following components in parts by mass:

5-13 parts of methyl methacrylate,

Butyl acrylate 15-25 parts,

Styrene 7-16 parts,

15-30 parts of epoxy resin,

1-6 parts of methacrylic acid,

Acrylamide 1-5 parts,

1.5-2 parts of hydroxyethyl acrylate,

Emulsifier 0.5-5 parts,

Initiator 0.5-5 parts,

80-130 parts of deionized water,

Ammonia 0.1-1 part.

It is prepared by mixing component A and component B respectively, and then stirring and mixing component A and component B in a mass ratio of 8-16:1.

Further, the conductive polymer material includes polyaniline, polythiophene, polypyrrole and derivatives thereof.

Further, the preparation of the conductive polymer/fullerene composite material includes the following steps:

(1) According to the ratio of polyaniline, polythiophene, polypyrrole and its derivative monomers to fullerene, add fullerene to hydrochloric acid solution, and carry out ultrasonic dispersion, add polyaniline, polythiophene, polypyrrole and Its derivative monomer is mixed uniformly to obtain mixed solution A;

(2) According to the ratio of oxidant to polyaniline, polythiophene, polypyrrole and its derivative monomers, dissolve oxidant ammonium persulfate or potassium persulfate into hydrochloric acid solution to obtain mixed solution B;

(3) Add mixed solution B to mixed solution A, mix evenly, centrifuge, wash until the filtrate is colorless, dry and grind the obtained precipitate to obtain a conductive polymer/fullerene composite material.

Further, the preparation of the conductive polymer/fullerene composite material includes the following steps:

(1) According to the mass ratio of polyaniline, polythiophene, polypyrrole and its derivative monomers and fullerenes of 1:5-95, add fullerenes to the hydrochloric acid solution, carry out ultrasonic dispersion, add polyaniline , polythiophene, polypyrrole and its derivatives monomers, control the concentration of polyaniline, polythiophene, polypyrrole and its derivatives monomers to be 0.03-0.28mol/L, the concentration of fullerenes to be 0.1-4mg/ml, and the concentration of hydrochloric acid to be is 0.1-1 mol/L, and mixes uniformly at 0-5 °C to obtain mixed solution A;

(2) According to the substance ratio of oxidant to polyaniline, polythiophene, polypyrrole and its derivative monomers is 1:0.5-2, dissolve oxidant ammonium persulfate or potassium persulfate into hydrochloric acid solution to obtain mixed solution B ;

(3) Add mixed solution B to mixed solution A, mix evenly at 0-5°C, react for 12-24 hours, stand for 6-12 hours, centrifuge, and wash with absolute ethanol and deionized water in turn until the filtrate is colorless , the obtained precipitate was vacuum-dried at 50 °C for 24 h, and ground to obtain a conductive polymer/fullerene composite material.

Further, the water-based curing agent is a water-based isocyanate curing agent;

The defoamer is at least one of a non-silicon defoamer, a polyether defoamer, and an organic silicon defoamer;

The wetting and dispersing agent is at least one of SN-5040, SN-5027, X-450, SC-860 and SP-710;

The adhesion promoter is an epoxy silane coupling agent;

The anti-flash rust agent is a chelated zinc compound water-based anti-flash rust agent;

The anti-settling thixotropic agent is at least one of polyamide wax, organic bentonite and fumed silica;

The leveling agent is an organosilicon leveling agent;

The anti-rust pigment is at least one of zinc phosphate, iron-titanium powder, titanium dioxide, and aluminum tripolyphosphate;

The zinc powder is 400 mesh, 600 mesh or 800 mesh.

Further, the emulsifier is a mixture of a nonionic emulsifier and an anionic emulsifier, and the mass ratio of the nonionic emulsifier to an anionic emulsifier is 1-2:1; the initiator is ammonium persulfate or sodium persulfate. a kind of.

The preparation method of a water-based anti-corrosion coating of the present invention comprises the following steps:

(1) Add water-based isocyanate curing agent, defoamer, dispersant, adhesion promoter and anti-flash rust agent into the paint tank according to the weight ratio of component A, mix, and stir;

(2) Add anti-settling thixotropic agent and leveling agent, stir; add anti-rust pigment and conductive polymer/fullerene composite material, stir; add zinc powder, stir and grind to obtain component A;

(3) According to the weight ratio of component B, mix 70-90% deionized water, 30-60% initiator, 25-50% emulsifier, epoxy resin, methyl methacrylate, butyl acrylate, Styrene, methacrylic acid monomer, acrylamide and hydroxyethyl acrylate are added to reactor A, and dispersed to obtain polymerized monomer pre-emulsion;

(4) Under the condition of room temperature and stirring, add 5-10% of the polymerized monomer pre-emulsion and the remainder of the emulsifier in the reactor B, heat up, add 5-10% of the residual deionized solution The initiator aqueous solution formed by mixing water and the remaining initiator is kept warm until blue light appears in the reactor to obtain the seed emulsion;

(5) adding the remainder of the polymerized monomer pre-emulsion dropwise to the seed emulsion, then adding the remainder of the initiator aqueous solution at regular intervals, after the insulation reaction, cooling to room temperature, adding ammonia water, Filter to obtain component B;

(6) Component B is added to component A in a stirring state for mixing treatment and stirring to obtain a water-based anti-corrosion coating.

The preparation method of a water-based anti-corrosion coating of the present invention comprises the following steps:

(1) Add water-based isocyanate curing agent, defoamer, dispersant, adhesion promoter and anti-flash rust agent to the paint tank according to the weight ratio of component A, and stir for 10-15 minutes;

(2) Add anti-settling thixotropic agent and leveling agent, stir for 15-20 minutes; add anti-rust pigment and conductive polymer/fullerene composite material, stir for 1-2 hours; add zinc powder, stir for 10-15 minutes, grind, to obtain component A;

(3) According to the weight ratio of component B, mix 70-90% deionized water, 30-60% initiator, 25-50% emulsifier, epoxy resin, methyl methacrylate, butyl acrylate, Styrene, methacrylic acid monomer, acrylamide and hydroxyethyl acrylate are added to reactor A, and dispersed for 30-40min to obtain polymerized monomer pre-emulsion;

(4) Under the condition of room temperature and stirring, add 5-10% of the polymerized monomer pre-emulsion and the remaining part of the emulsifier into the reactor B, heat it up to 75-80 ℃, add 5-10% by The initiator aqueous solution formed by mixing the remaining deionized water and the remaining initiator is kept at a temperature of 30-40min until blue light appears in the reactor to obtain a seed emulsion;

(5) The remaining part of the polymerized monomer pre-emulsion is added dropwise to the seed emulsion, and the dropping time is 2-3h, and then the remaining part of the initiator aqueous solution is added every fixed time, 75-80 Incubate the reaction at ℃ for 2h, cool down to room temperature, add ammonia water, and filter to obtain component B;

(6) According to the mass ratio, the component B is added to the component A in the stirring state for mixing treatment, and stirring for 30-40min, that is, the water-based anti-corrosion coating is obtained.

Further, in the step (1), the stirring rate is 300-500r/min, in the step (2), the stirring rate for the first time is 300-500r/min; the stirring rate for the second time is 700-900r/min min; the third stirring speed is 400-700r/min.

Further, in the step (3), the stirring rate of dispersion is 1000-1200r/min; in the step (4), the stirring rate is 700-800r/min; in the step (6), the stirring rate is 900-1200r/min.

The beneficial effects produced by the above technical solutions are:

(1) The conductive polymer/fullerene composite material has good electrical conductivity, which reduces the zinc powder content required to maintain the overlap of zinc powder particles required by zinc powder in zinc-rich coatings to exert "cathodic protection", thereby overcoming traditional The zinc content of the solvent-based zinc-rich primer is too high, resulting in the reduction of the toughness and adhesion of the zinc-rich coating, and the disadvantages of being volatile during welding and polluting the environment. It has the characteristics of green environmental protection, good flexibility and strong adhesion;

(2) The large specific surface area of fullerenes can increase the diffusion length of aggressive gases (such as O ₂ and H ₂ O) in the coating, and significantly enhance the shielding performance of the coating, resulting in stronger anti-corrosion performance. , Fullerene is spherical structure, compared with other sheet shielding materials (such as graphene, carbon nanotubes and nano-montmorillonite), there is no problem of dispersion orientation, and it has stronger shielding performance;

(3) The conductive polymer has a "passivation" effect on the metal surface, which can improve the corrosion potential of the metal and enhance the anti-corrosion ability;

(4) The preparation method of the water-based anti-corrosion coating has the advantages of simple process and convenient operation.

Description of drawings

In order to illustrate the technical solutions in the embodiments of the present invention more clearly, the following briefly introduces the drawings required in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort.

Fig. 1 is the coating corrosion potential characterization diagram of the water-based anti-corrosion coatings prepared by Examples 1-4 of the present invention;

In the figure, 1: Example 1; 2: Example 2; 3: Example 3; 4: Example 4.

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

The embodiments of the present invention provide a water-based anti-corrosion coating and a preparation method thereof. The conductive polymer/fullerene composite modified water-based anti-corrosion coating is prepared by stirring and mixing component A and component B uniformly; the component A Including the following components: water-based isocyanate curing agent, zinc powder, defoaming agent, wetting and dispersing agent, anti-settling thixotropic agent, conductive polymer/fullerene composite material, anti-flash rust agent, leveling agent, adhesion promoter agent, anti-rust pigment.

Preferably, the curing agent is at least one of water-based isocyanate curing agents BA305, XP2451, and XP 2487, and BA305 is a cross-linking agent for water-based paints. Even under pre-dilution conditions, the coating film is still transparent and bright; XP 2451 and XP 2487 is used as a curing agent component for waterborne two-component coatings and sealers, and as an additive to enhance the performance of waterborne coating systems.

Preferably, the zinc powder has extremely strong covering power. It has good anti-rust and atmospheric corrosion resistance, 400-mesh, 600-mesh or 800-mesh zinc powder is convenient to disperse in the coating system.

Preferably, the defoamer EL-2607 is a non-silicon defoamer, which has strong defoaming ability, can solve the problem of difficult defoaming in the system, inhibit the introduction of air bubbles during stirring, and help tiny air bubbles from Released in coatings; DF-114 and DF-103, polyether defoamer, show outstanding performance and no toxicity to organisms and bacteria, with unparalleled foam control; LY-111 silicone defoamer is With modified polysiloxane as the main component, it can be used in many water-based environments to eliminate and suppress foam.

Preferably, the wetting and dispersing agent SN-5040 is an anionic surfactant with excellent wetting and dispersing properties. Low foaming, can improve the fluidity of the coating, and has excellent performance of stabilizing the viscosity of the slurry; SN-5027 is a polymer dispersant of hydrophobically modified ammonium polyacrylate, which can reduce the viscosity of the abrasive and improve the storage stability of the coating. It has the characteristics of increasing gloss and leveling; X-450 has a very strong wetting effect, which can avoid the coagulation of pigments and fillers and enhance the stability; SC-860 is a general dispersant for sodium polyacrylate, which is a high-efficiency inorganic pigment. Filler dispersant, with good viscosity reduction effect and good heat resistance; SP-710 is an organic high molecular polymer containing a pigment-friendly group, which can obviously improve the dispersibility, anti-settling and storage stability of pigments, shorten the grinding time time, improve the adhesion and appearance quality of the paint film.

Preferably, the anti-settling thixotropic agent is at least one of polyamide wax, organic bentonite and fumed silica, and polyamide wax is a thixotropic additive with excellent thixotropic properties and excellent anti-flow properties. Hanging ability and anti-settling ability; Organobentonite can form gel in various organic solvents, oils and liquid resins, and has good thickening, thixotropy, suspension stability, high temperature stability, lubricity, and film-forming properties. , water resistance and chemical stability; fumed silica has chemical inertness and special thixotropic properties, and is used as an additive for anti-settling, thickening and anti-sagging.

Preferably, the conductive polymer/fullerene composite material has good electrical conductivity, which reduces the zinc powder content required to maintain the overlap of the zinc powder particles required by the zinc powder in the zinc-rich coating to exert "cathodic protection", thereby Overcome the shortcomings of traditional solvent-based zinc-rich primers with high zinc content, resulting in reduced toughness and adhesion of zinc-rich coatings, volatile during welding and polluting the environment. ₂ and H ₂ O) diffusion length in the coating, which significantly enhances the shielding performance of the coating, resulting in stronger anti-corrosion performance. Compared with alkene, carbon nanotubes and nano-montmorillonite), there is no problem of dispersion orientation and has stronger shielding performance.

Preferably, the anti-flash rust agent is ZT-709 water-based anti-flash rust agent, the main component is a chelated zinc compound, which can prevent the formation of "flash rust" of water-soluble coatings, and can improve the anti-rust performance and salt resistance of the coatings. fog effect.

Preferably, the leveling agent is an organic silicon leveling agent SN-612, which improves the surface tension of the coating film, achieves a balance of surface tension, is beneficial to the flow and leveling of the coating film, and eliminates surface defects.

Preferably, the adhesion promoter is an epoxy silane coupling agent, and the kh550 molecule contains two different active groups, amino and oxygen, which are used to couple organic polymers and inorganic fillers to enhance their adhesion. ; kh560 improves the adhesion of inorganic fillers, substrates and resins to improve their physical properties, especially the mechanical strength, water resistance, electrical properties, heat resistance and other properties of composite materials, and has a high retention in wet state. rate; kh570 is mainly used to improve the surface adhesion of organic materials and inorganic materials, etc.; A-150 improves adhesion, heat resistance and water resistance.

Preferably, the anti-rust pigment is at least one of zinc phosphate, iron-titanium powder, titanium dioxide, aluminum tripolyphosphate, zinc phosphate, colorless orthorhombic crystal or white microcrystalline powder, used for the production of water-soluble coatings and Non-toxic anti-rust pigment; iron-titanium powder, strong adhesion, excellent anti-rust performance; titanium dioxide, can protect the stability of the medium, and can enhance the mechanical strength and adhesion of the paint film, prevent cracks, and prevent ultraviolet rays It can penetrate with water and prolong the life of the paint film; aluminum tripolyphosphate is a new generation of pollution-free white anti-rust pigments. Rust ability.

The water-based anti-corrosion coating provided by the invention has the advantages of strong shielding property, excellent anti-corrosion performance, environmental protection, good flexibility and strong adhesion, and the preparation method of the water-based anti-corrosion coating is simple and convenient.

In order to better illustrate the water-based anti-corrosion coatings provided in the embodiments of the present invention, further examples are given below through examples.

Example 1

In parts by mass, the raw material formula of component A consists of: 15 parts of BA305, 55 parts of 400 mesh zinc powder, 5 parts of EL-2607, 5 parts of SN-5040, 2 parts of organic bentonite, 2 parts of conductive polymer/fullerene parts, 0.5 parts of ZT-709, 0.5 parts of SN-612, 3 parts of kh560, and 10 parts of zinc phosphate. The raw material formula of component B consists of: 6 parts of methyl methacrylate, 20 parts of butyl acrylate, 16 parts of styrene, 15 parts of epoxy resin, 1 part of methacrylic acid, 1 part of acrylamide, and 1.5 parts of hydroxyethyl acrylate , 1.5 parts of emulsifier, 4 parts of initiator, 120 parts of deionized water, and 0.4 part of ammonia water.

Follow the steps below to prepare water-based anti-corrosion coatings

Step 1. Add the fullerene into the hydrochloric acid solution, and carry out ultrasonic dispersion for 1 hour. After the dispersion is uniform, add polyaniline, polythiophene, polypyrrole and its derivative monomers, and stir and mix evenly at 0-5 °C. is 300 r/min to obtain mixed solution A; the monomer concentration of polyaniline, polythiophene, polypyrrole and its derivatives is controlled to be 0.03 mol/L, the concentration of fullerene is 0.6 mg/ml, and the concentration of hydrochloric acid is 0.5 mol/L; After dissolving the oxidant into the hydrochloric acid solution, the mixed solution B is obtained; the mixed solution B is added to the mixed solution A, stirred and mixed evenly at 0-5 ℃, the stirring speed is 300r/min, the reaction is carried out for 12 hours, and the mixture is left standing for 6 hours. Centrifugation, Wash with absolute ethanol (3*500ml) and deionized water (4*500ml) successively until the filtrate is colorless to obtain the conductive polymer/fullerene composite material. The obtained precipitate was vacuum-dried at 50° C. for 24 hours, and ground to obtain conductive polymer/fullerene composite powder; the oxidant was ammonium persulfate, and the oxidant was composed of polyaniline, polythiophene, polypyrrole and its derivative monomers. The quantity ratio is 1:0.5.

Step 2.

1) Preparation of component A

Add the water-based isocyanate curing agent, defoamer, dispersant, adhesion promoter and anti-flash rust agent into the paint tank according to the weight ratio and mix, stir at 300r/min, and stir for 10 minutes; after uniform dispersion, add anti-sinking contact Change agent, stir at 300r/min for 15 minutes; add anti-rust pigment and conductive polymer/fullerene composite material under the condition of 300r/min, stir at 700r/min, stir for 1 hour; add zinc powder, stir at 400r/min for 10min, Disperse evenly, grind finely and discharge, seal and store in a cool place away from light.

2) Preparation of component B

100 parts of water, 0.5 parts of emulsifier, 2 parts of initiator, 25 parts of epoxy resin, 6 parts of methyl methacrylate, 20 parts of butyl acrylate, 12 parts of styrene, 3 parts of The methacrylic acid monomer and 4 parts of acrylamide were added to the reactor A, and dispersed for 30 minutes at a stirring speed of 1000 r/min to obtain a pre-emulsion of the polymerized monomer. At room temperature and with a stirring speed of 700 r/min, add 10% of the prepared polymerized monomer pre-emulsion and 1 part of emulsifier to the reactor, then heat up to 75 ° C, add the initiator aqueous solution, and keep the temperature for 40 minutes until the reaction Blue light appeared in the device, and the seed emulsion was obtained. Then, the remaining part of the prepared polymerized monomer pre-emulsion was added to the seed emulsion prepared above at 80°C, and the dripping time was 3h, and then the initiator aqueous solution was added at regular intervals, and then at 80 °C. Incubate the reaction at ℃ for 2h, cool down to room temperature, add 0.4 part of ammonia water, filter, and discharge. Finally, the aqueous emulsion is stirred well.

The initiator aqueous solution is formed by mixing 2 parts of initiator and 20 parts of water.

3) The coating is a two-component combination of A and B, and the weight ratio is 8:1. During construction, stir the A component, add the B component during the stirring, stir at 900 r/min, stir for 30 minutes, and mix evenly , that is, water-based anti-corrosion coatings.

Example 2

In parts by mass, the raw material formula of component A consists of: 20 parts of XP2451, 15 parts of 600-mesh zinc powder, 1 part of DF-103, 1 part of SN-5040, 1 part of organic bentonite, 0.5 part of fumed silica, conductive 2.5 parts of polymer/fullerene composite material, 0.7 parts of ZT-709, 0.8 parts of SN-612, 3.5 parts of kh550, 10 parts of zinc phosphate, 5 parts of iron and titanium powder; component B is made of the following parts by mass: methyl 13 parts of methyl acrylate, 25 parts of butyl acrylate, 12 parts of styrene, 30 parts of epoxy resin, 6 parts of methacrylic acid, 5 parts of acrylamide, 2 parts of hydroxyethyl acrylate, 4 parts of emulsifier, 5 parts of initiator , 130 parts of deionized water, 0.4 parts of ammonia water.

Follow the steps below to prepare water-based anti-corrosion coatings

Step 1. Add the fullerene into the hydrochloric acid solution, and carry out ultrasonic dispersion for 30min. After the dispersion is uniform, add polyaniline, polythiophene, polypyrrole and its derivative monomers, and stir and mix evenly at 0-5 °C. is 300 r/min to obtain mixed solution A; the monomer concentration of polyaniline, polythiophene, polypyrrole and its derivatives is controlled to be 0.08 mol/L, the concentration of fullerene is 0.9 mg/ml, and the concentration of hydrochloric acid is 0.8 mol/L; After dissolving the oxidizing agent into the hydrochloric acid solution, the mixed solution B was obtained; the mixed solution B was added to the mixed solution A, stirred and mixed evenly at 0-5 ° C, the stirring speed was 300 r/min, the reaction was performed for 16 hours, and the mixture was left standing for 8 hours. Centrifugation, Wash with absolute ethanol (3*500ml) and deionized water (4*500ml) successively until the filtrate is colorless to obtain the doped polyaniline graphene oxide composite material. The obtained precipitate was vacuum-dried at 50° C. for 24 hours, and ground to obtain conductive polymer/fullerene composite powder; the oxidant was potassium persulfate, and the oxidant was composed of polyaniline, polythiophene, polypyrrole and its derivative monomers. The quantity ratio is 1:0.8.

Step 2.

1) Preparation of component A

Add water-based isocyanate curing agent, defoamer, dispersant, adhesion promoter and anti-flash rust agent into the paint tank according to the weight ratio and mix, stir at 400r/min, and stir for 15 minutes; after uniform dispersion, add anti-sinking contact Change agent, stir at 400r/min for 15 minutes; add anti-rust pigment and conductive polymer/fullerene composite material under the condition of 400r/min, stir at 800r/min, stir for 1.5 hours; add zinc powder, stir at 400r/min for 15min, Disperse evenly, grind finely and discharge, seal and store in a cool place away from light.

2) Preparation of component B

100 parts of water, 1 part of emulsifier, 2 parts of initiator, 25 parts of epoxy resin, 6 parts of methyl methacrylate, 20 parts of butyl acrylate, 12 parts of styrene, 3 parts of The methacrylic acid monomer, 4 parts of acrylamide and 1.5 parts of hydroxyethyl acrylate were added to the reactor A, and dispersed for 30 minutes at a stirring speed of 1000 r/min to obtain a pre-emulsion of the polymerized monomer. At room temperature and with a stirring speed of 700 r/min, add 10% of the prepared polymerized monomer pre-emulsion and 3 parts of emulsifier to the reactor, then heat up to 75 ° C, add the initiator aqueous solution, and keep the temperature for 40 minutes until the reaction Blue light appeared in the device, and the seed emulsion was obtained. Then, the remaining part of the prepared polymerized monomer pre-emulsion was added to the seed emulsion prepared above at 80°C, and the dripping time was 3h, and then the initiator aqueous solution was added at regular intervals, and then at 80 °C. Incubate the reaction at ℃ for 2h, cool down to room temperature, add 0.4 part of ammonia water, filter, and discharge. Finally, the aqueous emulsion is stirred well.

The initiator aqueous solution is formed by mixing 3 parts of initiator and 30 parts of water.

3) The coating is a two-component combination of A and B, and the weight ratio is 10:1. During construction, stir the A component, add the B component during the stirring, stir at 900 r/min, stir for 30 minutes, and mix evenly , that is, water-based anti-corrosion coatings.

Example 3

In parts by mass, the raw material formula of component A consists of: 25 parts of XP2451, 35 parts of 800 mesh zinc powder, 5 parts of DF-114, 1 part of SN-5040, 2 parts of polyamide wax, conductive polymer/fullerene 4 parts of composite material, 0.8 part of ZT-709, 1 part of SN-612, 1 part of kh560, 2.5 parts of zinc phosphate, 2.5 parts of aluminum tripolyphosphate; the raw material formula of component B is: 6 parts of methyl methacrylate, acrylic acid 20 parts of butyl ester, 12 parts of styrene, 25 parts of epoxy resin, 3 parts of methacrylic acid, 4 parts of acrylamide, 1.5 parts of hydroxyethyl acrylate, 1.5 parts of emulsifier, 2 parts of initiator, 80 parts of deionized water, Ammonia 0.4 parts.

Follow the steps below to prepare water-based anti-corrosion coatings

Step 1. Add the fullerene into the hydrochloric acid solution, and carry out ultrasonic dispersion for 1.5 hours. After the dispersion is uniform, add polyaniline, polythiophene, polypyrrole and its derivative monomers, stir and mix at 0-5 °C, and stir. The speed is 300r/min, and the mixed solution A is obtained; the monomer concentration of polyaniline, polythiophene, polypyrrole and its derivatives is controlled to be 0.1mol/L, the concentration of fullerene is 1.2mg/ml, and the concentration of hydrochloric acid is 0.9mol/L ; After dissolving the oxidant in the hydrochloric acid solution, the mixed solution B was obtained; The mixed solution B was added to the mixed solution A, stirred and mixed evenly at 0-5°C, the stirring speed was 300r/min, the reaction was performed for 18 hours, left standing for 10 hours, and centrifuged , washed with absolute ethanol (3*500ml) and deionized water (4*500ml) successively until the filtrate was colorless, and the conductive polymer/fullerene composite material was obtained. The obtained precipitate was vacuum-dried at 50° C. for 24 hours, and ground to obtain conductive polymer/fullerene composite powder; the oxidant was ammonium persulfate, and the oxidant was composed of polyaniline, polythiophene, polypyrrole and its derivative monomers. The quantity ratio is 1:1.1.

Step 2.

1) Preparation of component A

Add the water-based isocyanate curing agent, defoamer, dispersant, adhesion promoter and anti-flash rust agent into the paint tank according to the weight ratio, stir at 500 r/min, and stir for 15 minutes; after uniform dispersion, add anti-sinking contact Change agent, stir at 500r/min for 20 minutes; add anti-rust pigment and conductive polymer/fullerene composite material under the condition of 500r/min, stir at 900r/min, stir for 1-2 hours; add zinc powder, stir at 700r/min 15min, disperse evenly, grind finely and discharge, seal and store in a cool place away from light.

2) Preparation of component B

70 parts of water, 0.5 parts of emulsifier, 1 part of initiator, 25 parts of epoxy resin, 6 parts of methyl methacrylate, 20 parts of butyl acrylate, 12 parts of styrene, 3 parts of The methacrylic acid monomer, 4 parts of acrylamide and 1.5 parts of hydroxyethyl acrylate were added to the reactor A, and dispersed for 30 minutes at a stirring speed of 1000 r/min to obtain a pre-emulsion of the polymerized monomer. At room temperature and with a stirring speed of 700 r/min, add 10% of the prepared polymerized monomer pre-emulsion and 1 part of emulsifier to the reactor, then heat up to 75 ° C, add the initiator aqueous solution, and keep the temperature for 40 minutes until the reaction Blue light appeared in the device, and the seed emulsion was obtained. Then, the remaining part of the prepared polymerized monomer pre-emulsion was added to the seed emulsion prepared above at 80°C, and the dripping time was 3h, and then the initiator aqueous solution was added at regular intervals, and then at 80 °C. Incubate the reaction at ℃ for 2h, cool down to room temperature, add 0.4 part of ammonia water, filter, and discharge. Finally, the aqueous emulsion is stirred well.

The initiator aqueous solution is prepared by mixing 1 part of initiator and 10 parts of water.

3) The coating is a two-component combination of A and B, and the weight ratio is 12:1. During construction, stir the A component, add the B component during the stirring, stir at 1200 r/min, stir for 40 minutes, and mix evenly , that is, water-based anti-corrosion coatings.

Example 4

In parts by mass, the raw material formula of component A consists of: 15 parts of XP2487, 29 parts of 600 mesh zinc powder, 4 parts of EL-2607, 3 parts of SN-5040, 2 parts of organic bentonite, conductive polymer/fullerene composite 0.1 part of materials, 1 part of ZT-709, 0.5 part of SN-6120, 2 parts of A-150, 2.5 parts of iron-titanium powder, 3.5 parts of aluminum tripolyphosphate; the raw material formula of component B is: 5 parts of methyl methacrylate, 15 parts of butyl acrylate, 7 parts of styrene, 25 parts of epoxy resin, 3 parts of methacrylic acid, 4 parts of acrylamide and 1.5 parts of hydroxyethyl acrylate, 0.5 parts of emulsifier, 0.5 parts of initiator, 80 parts of deionized water , 0.1 part of ammonia water.

Follow the steps below to prepare water-based anti-corrosion coatings

Step 1. Add the fullerene into the hydrochloric acid solution, and carry out ultrasonic dispersion for 1.5 hours. After the dispersion is uniform, add polyaniline, polythiophene, polypyrrole and its derivative monomers, stir and mix at 0-5 °C, and stir. The speed is 300r/min, and the mixed solution A is obtained; the monomer concentration of polyaniline, polythiophene, polypyrrole and its derivatives is controlled to be 0.25mol/L, the concentration of fullerene is 5mg/ml, and the concentration of hydrochloric acid is 1mol/L; After the oxidant is dissolved in the hydrochloric acid solution, the mixed solution B is obtained; the mixed solution B is added to the mixed solution A, stirred and mixed evenly at 0-5 ° C, the stirring speed is 300 r/min, the reaction is 24 hours, and it is left to stand for 12 hours. Centrifugation, followed by Wash with absolute ethanol (3*500ml) and deionized water (4*500ml) until the filtrate is colorless to obtain the conductive polymer/fullerene composite material. The obtained precipitate was vacuum-dried at 50° C. for 24 hours, and ground to obtain conductive polymer/fullerene composite powder; the oxidant was potassium persulfate, and the oxidant was composed of polyaniline, polythiophene, polypyrrole and its derivative monomers. The quantity ratio is 1:1.4.

Step 2.

1) Preparation of component A

Add the water-based isocyanate curing agent, defoamer, dispersant, adhesion promoter and anti-flash rust agent into the paint tank according to the weight ratio and mix, stir at 300r/min, and stir for 10 minutes; after uniform dispersion, add anti-sinking contact Change agent, stir at 500r/min for 20 minutes; add anti-rust pigment and conductive polymer/fullerene composite material under the condition of 300r/min, stir at 700r/min, stir for 1-2 hours; add zinc powder, stir at 600r/min 15min, disperse evenly, grind finely and discharge, seal and store in a cool place away from light.

2) Preparation of component B

70 parts of water, 0.2 parts of emulsifier, 0.2 parts of initiator, 25 parts of epoxy resin, 6 parts of methyl methacrylate, 20 parts of butyl acrylate, 12 parts of styrene, 3 parts of The methacrylic acid monomer, 4 parts of acrylamide and 1.5 parts of hydroxyethyl acrylate were added to the reactor A, and dispersed for 30 minutes at a stirring speed of 1000 r/min to obtain a pre-emulsion of the polymerized monomer. At room temperature and a stirring speed of 700 r/min, add 10% of the prepared polymerized monomer pre-emulsion and 0.3 part of emulsifier to the reactor, then heat up to 75 ° C, add the initiator aqueous solution, and keep the temperature for 40 minutes until the reaction Blue light appeared in the device, and the seed emulsion was obtained. Then, the remaining part of the prepared polymerized monomer pre-emulsion was added to the seed emulsion prepared above at 80 ° C, the dripping time was 3h, and then the initiator aqueous solution was added at regular intervals, and then at 80 Incubate the reaction at ℃ for 2h, cool down to room temperature, add 0.4 part of ammonia water, filter, and discharge. Finally, the aqueous emulsion is stirred well.

The initiator aqueous solution is prepared by mixing 0.3 parts of initiator and 10 parts of water.

3) The coating is a two-component combination of A and B, and the weight ratio is 14:1. During construction, stir the A component, add the B component during the stirring, stir at 1200 r/min, stir for 40 minutes, and mix evenly , that is, water-based anti-corrosion coatings.

Example 5

In parts by mass, the raw material formula of component A consists of: 25 parts of XP2487, 29 parts of 400 mesh zinc powder, 1 part of DF-103, 5 parts of SN-5040, 0.9 part of fumed silica, conductive polymer/Fuller 5 parts of olefin composite material, 1 part of ZT-709, 1 part of SN-612, 1 part of kh570, 1.5 parts of aluminum tripolyphosphate, 2 parts of zinc phosphate, 2.5 parts of iron and titanium powder; component B raw material formula is composed of: methyl 6 parts of methyl acrylate, 20 parts of butyl acrylate, 12 parts of styrene, 25 parts of epoxy resin, 3 parts of methacrylic acid, 4 parts of acrylamide, 1.5 parts of hydroxyethyl acrylate, 5 parts of emulsifier, 4 parts of initiator , 120 parts of deionized water, and 1 part of ammonia water.

Follow the steps below to prepare water-based anti-corrosion coatings

Step 1. Add the fullerene into the hydrochloric acid solution, and carry out ultrasonic dispersion for 2 hours. After the dispersion is uniform, add polyaniline, polythiophene, polypyrrole and its derivative monomers, and stir and mix evenly at 0-5 °C. is 300 r/min to obtain mixed solution A; the monomer concentration of polyaniline, polythiophene, polypyrrole and its derivatives is controlled to be 0.28 mol/L, the concentration of fullerene is 2.5 mg/ml, and the concentration of hydrochloric acid is 0.6 mol/L; After dissolving the oxidant in the hydrochloric acid solution, the mixed solution B was obtained; the mixed solution B was added to the mixed solution A, stirred and mixed evenly at 0-5 ° C, the stirring speed was 300 r/min, the reaction was performed for 24 hours, and the mixture was left standing for 12 hours. Centrifugation, Wash with absolute ethanol (3*500ml) and deionized water (4*500ml) successively until the filtrate is colorless to obtain the conductive polymer/fullerene composite material. The obtained precipitate was vacuum-dried at 50° C. for 24 hours, and ground to obtain conductive polymer/fullerene composite powder; the oxidant was ammonium persulfate, and the oxidant was composed of polyaniline, polythiophene, polypyrrole and its derivative monomers. The quantity ratio is 1:1.4.

Step 2.

1) Preparation of component A

Add the water-based isocyanate curing agent, defoamer, dispersant, adhesion promoter and anti-flash rust agent into the paint tank according to the weight ratio and mix, stir at 300r/min, and stir for 10 minutes; after uniform dispersion, add anti-sinking contact Change agent, stir at 500r/min for 20 minutes; add anti-rust pigment and conductive polymer/fullerene composite material under the condition of 300r/min, stir at 700r/min, stir for 1-2 hours; add zinc powder, stir at 600r/min 15min, disperse evenly, grind finely and discharge, seal and store in a cool place away from light.

2) Preparation of component B

100 parts of water, 1.5 parts of emulsifier, 2 parts of initiator, 25 parts of epoxy resin, 6 parts of methyl methacrylate, 20 parts of butyl acrylate, 12 parts of styrene, 3 parts of The methacrylic acid monomer, 4 parts of acrylamide and 1.5 parts of hydroxyethyl acrylate were added to the reactor A, and dispersed for 30 minutes at a stirring speed of 1000 r/min to obtain a pre-emulsion of the polymerized monomer. At room temperature and a stirring speed of 700 r/min, add 10% of the prepared polymerized monomer pre-emulsion and 3.5 parts of emulsifier to the reactor, then heat up to 75 ° C, add the initiator aqueous solution, and keep the temperature for 40 minutes until the reaction Blue light appeared in the device, and the seed emulsion was obtained. Then, the remaining part of the prepared polymerized monomer pre-emulsion was added to the seed emulsion prepared above at 80°C, and the dripping time was 3h, and then the initiator aqueous solution was added at regular intervals, and then at 80 °C. Incubate the reaction at ℃ for 2h, cool down to room temperature, add 0.4 part of ammonia water, filter, and discharge. Finally, the aqueous emulsion is stirred well.

The initiator aqueous solution is formed by mixing 2 parts of initiator and 20 parts of water.

3) The coating is a two-component combination of A and B, and the weight ratio is 16:1. During construction, stir the A component, add the B component during the stirring, stir at 1200 r/min, stir for 40 minutes, and mix evenly , that is, water-based anti-corrosion coatings.

The water-based anti-corrosion coatings prepared in the above Examples 1-5 were dark gray-black after curing, and the paint films were smooth and defect-free. At the same time, the products prepared in Examples 1-5 were tested for their performance, and the test results were shown in the following table.

From the above data, it can be seen that a water-based anti-corrosion coating and a preparation method thereof of the present invention, the provided conductive polymer/fullerene composite modified water-based anti-corrosion coating has good flexibility, adhesion, hardness, water resistance, The characteristics of salt water resistance and neutral salt spray resistance.

The corrosion potential of the coating obtained in Example 1-4 was characterized, as shown in Figure 1. It can be seen from Figure 1 that the corrosion potential of the coating in Example 1-4 is in Zn (-1.1) and Fe ( -0.54), the corrosion potential of the coating is closer to the corrosion potential of zinc, indicating that the water-based anti-corrosion coating prepared by the method of the present invention has a cathodic protection effect on the base iron and exerts anti-corrosion effect. The self-corrosion current of 1-4 first decreased and then increased. According to the principle that the smaller the self-corrosion current, the slower the corrosion rate of the sample, it can be seen that Example 2 has the best anti-corrosion performance.

Claims (8)

1. a kind of water-based anticorrosive paint, which is characterized in that including component A and component B；

The component A includes the following component of mass parts:

Conducting polymer/0.1-5 parts of fulvene compounding material, wherein the mass ratio of conductive polymer material and fullerene is 1: 5-95,

The component B includes the following component of mass parts:

It is after being mixed to prepare respectively by component A and component B, then by component A and component B with mass ratio is that 8-16:1 is stirred system ,

The conductive polymer material includes polyaniline, polythiophene, polypyrrole and its derivatives monomer, and the conducting polymer/ Fulvene compounding material is prepared with the following method:

It (1) is 1:5-95 according to the mass ratio of polyaniline, polythiophene, polypyrrole and its derivatives monomer and fullerene, by fowler Alkene is added in hydrochloric acid solution, and carries out ultrasonic disperse, and polyaniline, polythiophene, polypyrrole and its derivatives monomer, mixing is added Uniformly, mixed liquor A is obtained；

It (2) is 1:0.5-2 according to the mass ratio of the material of oxidant and polyaniline, polythiophene, polypyrrole and its derivatives monomer, it will Oxidant ammonium persulfate or potassium peroxydisulfate are dissolved into hydrochloric acid solution, obtain mixed liquid B；

(3) mixed liquid B is added in mixed solution A, is uniformly mixed, centrifugation, it is colourless for washing to filtrate, gained is precipitated dry Dry, grinding obtains conducting polymer/fulvene compounding material.

2. a kind of water-based anticorrosive paint according to claim 1, which is characterized in that the conducting polymer/fullerene is multiple The preparation of condensation material, includes the following steps:

It (1) is 1:5-95 according to the mass ratio of polyaniline, polythiophene, polypyrrole and its derivatives monomer and fullerene, by fowler Alkene is added in hydrochloric acid solution, and carries out ultrasonic disperse, and polyaniline, polythiophene, polypyrrole and its derivatives monomer, control is added Polyaniline, polythiophene, polypyrrole and its derivatives monomer concentration are 0.03-0.28mol/L, fullerene concentration 0.1-4mg/ Ml, concentration of hydrochloric acid 0.1-1mol/L are uniformly mixed at 0-5 DEG C, obtain mixed liquor A；

It (2) is 1:0.5-2 according to the mass ratio of the material of oxidant and polyaniline, polythiophene, polypyrrole and its derivatives monomer, it will Oxidant ammonium persulfate or potassium peroxydisulfate are dissolved into hydrochloric acid solution, obtain mixed liquid B；

(3) mixed liquid B is added in mixed solution A, is uniformly mixed at 0-5 DEG C, react 12-24h, stand 6-12h, be centrifuged, It is colourless for successively being washed with dehydrated alcohol, deionized water to filtrate, and gained is deposited at 50 DEG C and is dried in vacuo for 24 hours, grinding obtains To conducting polymer/fulvene compounding material.

3. a kind of water-based anticorrosive paint according to claim 1, which is characterized in that

The defoaming agent is at least one of non-silicon class defoaming agent, polyether antifoam agent, organic silicon defoamer；

The Ricinate is at least one of SN-5040, SN-5027, X-450, SC-860, SP-710；

The adhesion promoter is epoxy silane coupling；

The anti-flash rusting agent is the aqueous anti-flash rusting agent of chelated zinc compound；

The anti-settling thixotropic agent is at least one of polyamide wax, organobentonite and fumed silica；

The levelling agent is organosilicon levelling agent；

The rust resisting pigment is at least one of trbasic zinc phosphate, ferrotitanium powder, titanium dioxide, aluminium triphosphate；

The zinc powder is 400 mesh, 600 mesh or 800 mesh.

4. a kind of water-based anticorrosive paint according to claim 1, which is characterized in that the emulsifier is nonionic emulsifier With the mixture of anion emulsifier, the mass ratio of nonionic emulsifier and anion emulsifier is 1-2:1；The initiator is One of ammonium persulfate or sodium peroxydisulfate.

5. a kind of described in any item preparation methods of water-based anticorrosive paint of claim 1-4, which is characterized in that include following step It is rapid:

(1) component A weight ratio is pressed by water-based isocyanate curing agent, defoaming agent, Ricinate, adhesion promoter and anti-sudden strain of a muscle Rust agent is added to mixing in paint can, is stirred；

(2) anti-settling thixotropic agent, levelling agent, stirring is added；Rust resisting pigment and conducting polymer/fulvene compounding material is added, stirs It mixes；Zinc powder is added and stirs, grinds, obtains component A；

(3) component B weight ratio is pressed, by the deionized water of 70-90%, the initiator of 30-60%, the emulsifier of 25-50%, epoxy Resin, methyl methacrylate, butyl acrylate, styrene, methacrylic acid, acrylamide and hydroxy-ethyl acrylate are added to In reactor A, dispersion obtains polymerized monomer pre-emulsion；

(4) under room temperature and stirring, polymerized monomer pre-emulsion and the emulsification described in 5-10% are added in reactor B The initiation that 5-10% is mixed by the remaining deionized water and the remaining initiator is added in the remainder of agent, heating Agent aqueous solution, heat preservation obtain seed emulsion until there is blue light in reactor；

(5) remainder of the polymerized monomer pre-emulsion is added drop-wise in the seed emulsion, later every the set time It is added the remainder of the initiator solution, after insulation reaction, is cooled to room temperature, ammonium hydroxide is added, filtering obtains component B；

(6) component B is added in component A under stirring and carries out mixed processing, stirred to get water-based anticorrosive paint.

6. a kind of preparation method of water-based anticorrosive paint described in claim 5, which is characterized in that comprise the following steps:

(1) component A weight ratio is pressed by water-based isocyanate curing agent, defoaming agent, Ricinate, adhesion promoter and anti-sudden strain of a muscle Rust agent is added to mixing in paint can, is stirred 10-15 minutes；

(2) anti-settling thixotropic agent, levelling agent is added, stirs 15-20 minutes；Rust resisting pigment is added and conducting polymer/fullerene is multiple Condensation material stirs 1-2h；Zinc powder is added and stirs 10-15min, grinding obtains component A；

(3) component B weight ratio is pressed, by the deionized water of 70-90%, the initiator of 30-60%, the emulsifier of 25-50%, epoxy Resin, methyl methacrylate, butyl acrylate, styrene, methacrylic acid, acrylamide and hydroxy-ethyl acrylate are added to In reactor A, disperses 30-40min, obtain polymerized monomer pre-emulsion；

(4) under room temperature and stirring, polymerized monomer pre-emulsion and the emulsification described in 5-10% are added in reactor B The remainder of agent, is warming up to 75-80 DEG C, be added 5-10% mixed with the residue initiator by the remaining deionized water and At initiator solution, keep the temperature 30-40min, until reactor in there is blue light, obtain seed emulsion；

(5) remainder of the polymerized monomer pre-emulsion is added drop-wise in the seed emulsion, time for adding 2-3h, it The remainder of the initiator solution is added every the set time afterwards, insulation reaction 2h at 75-80 DEG C is cooled to room temperature, Ammonium hydroxide is added, filtering obtains component B；

(6) according to mass ratio, component B is added in component A under stirring and carries out mixed processing, stir 30-40min, Up to water-based anticorrosive paint.

7. a kind of preparation method of water-based anticorrosive paint according to claim 6, which is characterized in that in the step (1), Stirring rate is 300-500r/min, and in the step (2), first time stirring rate is 300-500r/min；Second of stirring Rate is 700-900r/min；Third time stirring rate is 400-700r/min.

8. a kind of preparation method of water-based anticorrosive paint according to claim 6, which is characterized in that in the step (3), The stirring rate of dispersion is 1000-1200r/min；In the step (4), stirring rate 700-800r/min；The step (6) in, stirring rate 900-1200r/min.