A water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating and preparation method thereof

Abstract

The present invention discloses a water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating and a preparation method thereof, a water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating, the raw materials used include 100 parts of water-based resin and 5-20 parts of hollow fibers of a polymer cross-linked network structure, the parts are by mass; wherein the water-based resin is at least one of a composite of a water-based epoxy resin and an epoxy curing agent, a water-based acrylate emulsion, a water-based polyurethane emulsion or a water-based polyurethane-acrylate emulsion. The self-repairing coating obtained by the present invention has a smooth and uniform surface, bright color, stable structure, good thermal stability, strong water resistance, excellent mechanical properties, and excellent adhesion, corrosion resistance, wear resistance and self-repairing properties.

Description

Technical Field

[0001] The invention relates to a water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating and a preparation method thereof, belonging to the technical field of intelligent coatings. Background Art

[0002] Metal corrosion is a common phenomenon in life and production, and metal coating anti-corrosion is one of the most effective ways to prevent metal corrosion. The research on anti-corrosion coating materials has evolved from the initial passive anti-corrosion, that is, only playing the physical isolation role of the coating to prevent the metal substrate from direct contact with the corrosive medium in the environment, to today's combination of passive anti-corrosion and active anti-corrosion, that is, when the coating is damaged, it can continue to play an active anti-corrosion role and reduce the corrosion rate of the protected metal. At present, a large number of studies are focused on the preparation of various novel structural corrosion inhibitor carrier materials, such as hollow, mesoporous organic or inorganic materials. While efficiently loading the corrosion inhibitor, the release rate of the corrosion inhibitor has also developed from uncontrollable one-time release to controllable release with stimulus responsiveness, making the coating anti-corrosion more "intelligent".

[0003] Patent CN 113292926 A discloses a water-based self-repairing epoxy anti-corrosion coating and its preparation method, the raw materials are as follows: modified epoxy resin, epoxy emulsifier, deionized water, modified zinc phosphate, water-based curing agent, anti-flash rust agent and defoaming agent. The invention has the advantages of strong self-repairing ability of the coating, self-repairing at room temperature, high aging resistance and anti-corrosion ability, and uniform coating. Patent CN 113831825 A discloses a self-repairing waterborne polyurethane anti-corrosion coating and its preparation method. The coating is prepared from the following components by weight: 0.002-0.005 parts of graphene oxide (GO), 20-50 parts of waterborne polyurethane emulsion (WPU), 5-20 parts of tung oil, 5-15 parts of polyvinyl alcohol (PVA), 1-10 parts of silane coupling agent, 1-10 parts of phosphoric acid, 0.01-0.4 parts of photoinitiator and 30-110 parts of deionized water; the solid content of the coating is 20-40%. The coating made of the self-repairing waterborne polyurethane anti-corrosion coating provided by the invention has a smooth and uniform surface, bright color, stable structure, good thermal stability, strong water resistance, excellent mechanical properties, excellent adhesion, corrosion resistance, wear resistance and self-repairing properties. Although the self-healing anti-corrosion coatings on the market have partially solved the material protection problem, we still have to face another inevitable problem, that is, in the actual working environment, the metal coating will be affected by environmental factors or external forces, resulting in various damages, such as microcracks, which gradually spread and expand, causing cracks in the coating, etc. In such cases, even with the presence of metal corrosion inhibitors, the service life and anti-corrosion ability of the coating become very limited, because once the corrosion inhibitor is released, the anti-corrosion ability is lost.

[0004] Therefore, there is an urgent need to develop a coating that can self-repair its own internal or external damage, thereby eliminating hidden dangers, greatly extending the service life of the coating, and achieving long-term anti-corrosion protection for metal substrates. Summary of the invention

[0005] In view of the above problems, the present invention proposes a bionic self-repairing, anti-fouling, anti-corrosion multifunctional coating and its preparation method, and introduces the design concept of active corrosion protection of metal corrosion inhibitors into the polymer hollow fiber shell system to achieve the goal of controlled release of corrosion inhibitors from polymer fibers. Combined with the "intrinsic" self-repairing core layer, a hollow fiber with dual functions of active corrosion protection and multiple self-repairing is obtained, and then compounded with an epoxy resin coating. If this composite coating is mechanically damaged, it will first release the self-repairing agent and part of the corrosion inhibitor to reach the damaged micro-area and form a barrier layer on the metal surface. Then, as the stimulation of the corrosive medium changes, a large amount of corrosion inhibitor will be actively and quickly released, further protecting the metal surface and exerting the dual functions of self-repairing and active corrosion protection.

[0006] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0007] A water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating, the raw materials used include 100 parts of water-based resin and 5-20 parts of hollow fibers with a polymer cross-linked network structure, the parts are by mass;

[0008] Wherein, the water-based resin is at least one of a composite of a water-based epoxy resin and an epoxy curing agent, a water-based acrylate emulsion, a water-based polyurethane emulsion or a water-based polyurethane-acrylate emulsion;

[0009] The method for preparing a hollow fiber with a polymer cross-linked network structure is carried out under light-proof conditions and comprises the following steps:

[0010] 1) dissolving chitosan in an acetic acid aqueous solution to obtain a chitosan acetic acid solution, and stirring the solution to obtain a solution 1; wherein the amount of the acetic acid aqueous solution required for 1 mol of chitosan is 2 to 2.2 L, and the content of acetic acid in the acetic acid aqueous solution is 0.5 to 0.6 mol / L;

[0011] 2) PEGDMA (polyethylene glycol dimethacrylate), 2-hydroxy-2-methyl-1-phenyl-1-propanone and DMAEMA (dimethylaminoethyl methacrylate) are uniformly mixed and added to the solution 1 prepared in step 1), and ultrasonic dispersion is performed to obtain a shell solution, and the shell solution is sucked into syringe A and fixed on a syringe pump, wherein the mass ratio of chitosan, PEGDMA, 2-hydroxy-2-methyl-1-phenyl-1-propanone and DMAEMA is 10: (4.5-5.5): (2.5-3.5): (9-11);

[0012] 3) dispersing the self-curing epoxy resin capable of multiple self-repairing in DMF, ultrasonically dispersing to obtain a core solution, and sucking the core solution into syringe B; wherein 2.8 to 3.1 mL of DMF is required for each gram of the self-curing epoxy resin capable of multiple self-repairing;

[0013] 4) Using a coaxial electrospinning method, the core solution and the shell solution are simultaneously pumped to an aluminum alloy plate collector using a coaxial electrospinning needle pump, and after DMF drying under medium-pressure mercury lamp irradiation, a hollow fiber with a polymer cross-linked network structure deposited on the surface of the aluminum alloy plate collector is obtained (the aluminum alloy plate collector is surface pretreated according to ASTM D1730-2009 before deposition).

[0014] In step 4), during coaxial electrospinning, the collection distance is 15-20 cm and the operating voltage is 10 kv-20 kv.

[0015] The entire solution preparation process and spinning process require protection from light.

[0016] In order to ensure the mechanical properties and self-repairing properties of the coating, in the above step 3), the method for preparing the self-curing epoxy resin capable of multiple self-repairing comprises the following steps:

[0017] 3.1) The maleimide monomer is prepared by reacting tert-butyl (2-aminoethyl)ethylcarbamate and maleic anhydride; the furan monomer is prepared by reacting furfurylamine and di-tert-butyl dicarbonate ((Boc)2O); and the DA crosslinking agent is prepared by reacting the maleimide monomer and the furan monomer;

[0018] 3.2) Self-curing DHTA-ECH epoxy resin is prepared by reacting p-hydroxyterephthalic acid (DHTA) with excess epichlorohydrin (ECH);

[0019] 3.3) A self-curing epoxy resin capable of multiple self-repairing is prepared by reacting a DA cross-linking agent with a self-curing DHTA-ECH epoxy resin.

[0020] The structural formula of the self-curable DHTA-ECH epoxy resin is:

[0021] The structural formula of DA crosslinker is

[0022] In the above step 3), the synthesis route of the self-curing epoxy resin that can self-repair multiple times is:

[0023]

[0024] In order to increase the yield of DA cross-linking agent, in the above step 3.1), the molar ratio of (2-aminoethyl)ethylcarbamate to maleic anhydride is 1:(1-1.2); the molar ratio of furfurylamine to di-tert-butyl dicarbonate is 1:(2-2.1); and the molar ratio of maleimide monomer to furan monomer is 1:(1-1.1).

[0025] Further preferably, step 3.1) the synthesis of the DA cross-linking agent comprises the following steps:

[0026] 3.1.1) Dissolve tert-butyl (2-aminoethyl)ethylcarbamate in dichloromethane, add maleic anhydride, then add acetone, acetic anhydride, triethylamine and nickel acetate tetrahydrate, react at room temperature to 100°C for 1-5 hours, separate, wash and purify to obtain a maleimide monomer partially protected by a Boc group; wherein the molar ratio of tert-butyl (2-aminoethyl)ethylcarbamate, maleic anhydride and nickel acetate tetrahydrate is 1:(1-1.2):(0.9-1.1);

[0027] 3.1.2) dissolving furfurylamine in dichloromethane, adding di-tert-butyl dicarbonate, reacting at room temperature to 80°C for 1-3 hours, separating, washing and purifying to obtain a furan monomer partially protected by a Boc group; wherein the molar ratio of furfurylamine to di-tert-butyl dicarbonate is 1:(2-2.2);

[0028] 3.1.3) The maleimide monomer obtained in step 1) and the furan monomer obtained in step 2) are dissolved in ethyl acetate (EtoAC), reacted at room temperature to 100°C for 1-12 hours, separated, washed and purified to obtain a DA cross-linking agent; wherein the molar ratio of the maleimide monomer to the furan monomer is 1: (1-1.2).

[0029] In order to improve the yield of self-curing DHTA-ECH epoxy resin, epichlorohydrin should be excessive. Preferably, in step 3.2), the molar ratio of hydroxyterephthalic acid (DHTA) to epichlorohydrin is 1: (1.1-1.2). More preferably, step 3.2) is to mix hydroxyterephthalic acid (DHTA), excess epichlorohydrin (ECH) and tetrabutylammonium iodide, stir and react at 80-150°C for 1-12 hours, slowly dropwise add excess sodium hydroxide solution (1 mol / L), wash, distill at normal pressure, extract and purify to obtain the self-curing DHTA-ECH epoxy resin.

[0030] The slow dripping speed of the present application is 30 to 60 drops / min.

[0031] In order to take into account both the mechanical properties and self-healing properties of the obtained film layer, in the above step 3.3), the mass ratio of the DA cross-linking agent to the self-curing DHTA-ECH epoxy resin is 1: (2 to 2.2). More preferably, step 3.3) is to mix the DA cross-linking agent with the self-curing DHTA-ECH epoxy resin at room temperature, vacuum degas, and then stir and react at 50-80°C for 1-5 hours to obtain a DA-EP epoxy resin; wherein the mass ratio of the DA cross-linking agent to the self-curing DHTA-ECH epoxy resin is 1: (2 to 2.2).

[0032] The vacuum degree of the above vacuum degassing is lower than -0.1MPa.

[0033] The preparation method of the above-mentioned water-based intelligent corrosion inhibition-self-repairing anti-corrosion composite coating is to mix the water-based resin and the hollow fiber of the polymer cross-linked network structure evenly, use a coating machine to spin coat it on the metal substrate, and cure it at room temperature to 100 degrees Celsius for 30 minutes to 24 hours to obtain the water-based intelligent corrosion inhibition-self-repairing anti-corrosion composite coating.

[0034] The technologies not mentioned in the present invention are all referred to the prior art.

[0035] The beneficial effects of the present invention are:

[0036] (1) Water-based coatings are not only green and environmentally friendly, but also have controllable coating structures. Different resins can be selected according to different usage environments. The coating thickness is controllable and the surface is smooth and uniform.

[0037] (2) Hollow fibers are coated with "intrinsic" self-healing agent materials. This type of hollow fiber can be applied to anti-corrosion coatings to achieve multiple self-healing functions.

[0038] (3) A DA cross-linking agent containing two secondary amine groups was synthesized and subjected to chain extension reaction with a self-curing epoxy resin to form a linear epoxy resin molecule based on a thermally reversible reaction. The linear epoxy resin molecule was then introduced into the core layer structure design of the polymer hollow fiber to prepare a polymer hollow fiber coated with an “intrinsic” single-component self-healing agent.

[0039] In summary, the self-repairing coating obtained by the present invention has a smooth and uniform surface, bright color, stable structure, good thermal stability, strong water resistance, excellent mechanical properties, and has excellent adhesion, corrosion resistance, wear resistance and self-repairing properties. DETAILED DESCRIPTION

[0040] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0041] In each case, the stirring speed was 200 r / min unless otherwise specified; the temperature was operated at room temperature (20-25° C.) unless otherwise specified.

[0042] Example 1

[0043] 1 mol of tert-butyl (2-aminoethyl)ethylcarbamate is dissolved in 50 mL of dichloromethane, 1 mol of maleic anhydride (MA) is added, and then 10 mL of acetone, 5 mL of acetic anhydride (AA), 5 ml of triethylamine, and 1 mol of nickel acetate tetrahydrate (NA) are added, and the mixture is reacted at 50° C. for 1 hour. After separation, washing, and purification, a maleimide monomer partially protected by a Boc group (tert-butyloxycarbonyl) is obtained;

[0044] Dissolve 1 mol of furfurylamine in 30 mL of dichloromethane, add 2 mol of di-tert-butyl dicarbonate ((Boc)2O) and react at 40°C for 1 hour, separate, wash and purify to obtain a furan monomer partially protected by a Boc group;

[0045] 1 mol of maleimide monomer and 1 mol of furan monomer were dissolved in ethyl acetate (EtoAC), reacted at 60° C. for 2 hours, and separated, washed, and purified to obtain a DA cross-linking agent.

[0046] Example 2

[0047] 1 mol of p-hydroxyterephthalic acid (DHTA), 2.1 mol of epichlorohydrin (ECH) and 1 mol of tetrabutylammonium iodide were mixed, stirred and reacted at 100°C for 2 hours, 1 mol / L of sodium hydroxide solution was slowly added dropwise (40 drops / min, 1 L was added dropwise), washed, distilled at normal pressure, extracted and purified to obtain a self-curing DHTA-ECH epoxy resin.

[0048] Example 3

[0049] 10 g of DA crosslinking agent (prepared in Example 1) and 21 g of DHTA-ECH epoxy resin (prepared in Example 2) were mixed at room temperature, vacuum degassed (vacuum degree lower than -0.1 MPa), and then stirred at 50° C. for 1.5 hours to obtain DA-EP epoxy resin.

[0050] Example 4

[0051] 10 g of chitosan was dissolved in 20 mL of acetic acid aqueous solution to obtain a chitosan acetic acid solution, and the solution was stirred evenly. Then, 5 g of PEGDMA (polyethylene glycol dimethacrylate, Mn=500, P432480, Aladdin), 3 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone (BASF, 1173D) and 10 g of DMAEMA were evenly mixed and added to the above solution, and ultrasonic dispersion was performed to obtain a shell solution, which was sucked into syringe A and fixed on the syringe pump; 10 g of DA-EP epoxy resin (prepared in Example 3) was dispersed in 30 mL of DMF, and ultrasonic dispersion was performed to obtain a core solution, which was sucked into syringe B. Hollow fibers were prepared by coaxial electrospinning. The collector was an aluminum alloy plate. The collection distance was 20 cm and the working voltage was 15 KV. The core solution and the shell solution were simultaneously pumped in by a coaxial needle. After the DMF was dried under medium-pressure mercury lamp irradiation, a hollow fiber with a polymer cross-linked network structure deposited on the surface of the aluminum alloy plate collector was obtained (the aluminum alloy plate was pre-treated according to ASTM D1730-2009 before deposition). The entire solution preparation process and spinning process required to be protected from light.

[0052] Example 5

[0053] After 100 g of aqueous acrylic emulsion Joncryl 8111AP and 10 g of hollow fibers with a polymer cross-linked network structure (prepared in Example 4) were evenly mixed, a self-healing coating was spin-coated on the surface of the aluminum alloy plate using a coating machine, and the coated aluminum alloy plate was placed in an oven for curing, thereby forming a composite coating on the surface of the aluminum alloy plate.

[0054] Example 6

[0055] After 100 g of aqueous polyurethane emulsion Dispercoll U2710 and 8 g of hollow fibers with a polymer cross-linked network structure (prepared with reference to Example 4) were evenly mixed, a self-healing coating was spin-coated on the surface of the aluminum alloy plate using a coating machine, and the coated aluminum alloy plate was placed in an oven for curing, thereby forming a composite coating on the surface of the aluminum alloy plate.

[0056] Example 7

[0057] After 100 g of aqueous polyurethane acrylate emulsion Joncryl OH 8312 and 10 g of hollow fibers with a polymer cross-linked network structure (prepared with reference to Example 4) were evenly mixed, a self-healing coating was spin-coated on the surface of the aluminum alloy plate using a coating machine, and the coated aluminum alloy plate was placed in an oven for curing, thereby forming a composite coating on the surface of the aluminum alloy plate.

[0058] Example 8

[0059] After mixing 100g of a mixture of water-containing epoxy resin agent PZ 3961-1 and 20g of a hollow fiber with a polymer cross-linked network structure (prepared with reference to Example 4) evenly, a self-healing coating was spin-coated on the surface of the aluminum alloy plate using a coating machine, and the coated aluminum alloy plate was placed in an oven for curing, thereby forming a composite coating on the surface of the aluminum alloy plate.

[0060] Example 9

[0061] After 100 g of aqueous polyurethane emulsion Dispercoll U2710 and 15 g of hollow fibers with a polymer cross-linked network structure (prepared with reference to Example 4) were evenly mixed, a self-healing coating was spin-coated on the surface of the aluminum alloy plate using a coating machine, and the coated aluminum alloy plate was placed in an oven for curing, thereby forming a composite coating on the surface of the aluminum alloy plate.

[0062] Example 10

[0063] After 100 g of aqueous polyurethane acrylate emulsion Joncryl OH 8312 and 12 g of hollow fibers with a polymer cross-linked network structure (prepared with reference to Example 4) were evenly mixed, a self-healing coating was spin-coated on the surface of the aluminum alloy plate using a coating machine, and the coated aluminum alloy plate was placed in an oven for curing, thereby forming a composite coating on the surface of the aluminum alloy plate.

[0064] The composite coatings obtained in the above examples have a smooth and uniform surface, bright color, stable structure, good thermal stability, strong water resistance, excellent mechanical properties, and have excellent adhesion, corrosion resistance, wear resistance, anti-fouling and self-repairing properties.

[0065] The coating was scratched with a blade (0.1 mm thickness), and the aluminum alloy plate without scratched coating and the scratched aluminum alloy plate were immersed in 0.1 mol / L NaCl solution respectively. The anti-corrosion performance of the coating was tested by an electrochemical workstation, and the performance was compared with the anti-corrosion performance of the pure aluminum alloy plate. As shown in Table X, the results show that the coating formed by the composite of waterborne polyurethane acrylate and polymer hollow fiber has excellent self-healing and anti-corrosion properties.

[0066] Table X Corrosion rate and corrosion inhibition efficiency (Tafel curve)

[0067]

Claims

1. A water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating, characterized by: The raw materials used include 100 parts of water-based resin and 5-20 parts of hollow fibers with a polymer cross-linked network structure, where the parts are by mass; Wherein, the water-based resin is at least one of a composite of a water-based epoxy resin and an epoxy curing agent, a water-based acrylate emulsion, a water-based polyurethane emulsion or a water-based polyurethane-acrylate emulsion; The method for preparing a hollow fiber with a polymer cross-linked network structure is carried out under light-proof conditions and comprises the following steps: 1) Dissolve chitosan in acetic acid aqueous solution to obtain chitosan acetic acid solution, and stir evenly to obtain solution 1; wherein the amount of acetic acid aqueous solution required for 1 mol of chitosan is 2-2.2 L, and the content of acetic acid in the acetic acid aqueous solution is 0.5-0.6 mol / L; 2) PEGDMA, 2-hydroxy-2-methyl-1-phenyl-1-propanone and DMAEMA are uniformly mixed and added to the solution 1 prepared in step 1), and ultrasonically dispersed to obtain a shell solution, and the shell solution is sucked into syringe A and fixed on the syringe pump, wherein the mass ratio of chitosan, PEGDMA, 2-hydroxy-2-methyl-1-phenyl-1-propanone and DMAEMA is 10: (4.5-5.5): (2.5-3.5): (9-11); 3) Dispersing the self-curing epoxy resin capable of multiple self-repairing in DMF, ultrasonically dispersing to obtain a core solution, and sucking the core solution into syringe B; wherein, 2.8-3.1 mL of DMF is required for each gram of the self-curing epoxy resin capable of multiple self-repairing; the self-curing epoxy resin capable of multiple self-repairing is a linear epoxy resin molecule based on a thermally reversible reaction formed by a chain extension reaction between a synthesized DA cross-linking agent containing two secondary amine groups and a self-curing epoxy resin; 4) The core solution and the shell solution are simultaneously pumped to an aluminum alloy plate collector by a coaxial electrospinning needle pump, and after DMF drying under medium-pressure mercury lamp irradiation, a hollow fiber with a polymer cross-linked network structure deposited on the surface of the aluminum alloy plate collector is obtained.

2. The water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating according to claim 1, characterized in that: In step 3), the method for preparing a self-curing epoxy resin capable of multiple self-repairing comprises the following steps: 3.1) The maleimide monomer is prepared by reacting tert-butyl (2-aminoethyl)ethylcarbamate with maleic anhydride; the furan monomer is prepared by reacting furfurylamine with di-tert-butyl dicarbonate; and the DA crosslinking agent is prepared by reacting the maleimide monomer with the furan monomer; 3.2) Self-curing DHTA-ECH epoxy resin is prepared by reacting p-hydroxyterephthalic acid with excess epichlorohydrin; 3.3) A self-curing epoxy resin capable of multiple self-repairing is prepared by reacting a DA cross-linking agent with a self-curing DHTA-ECH epoxy resin.

3. The water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating according to claim 2, characterized in that: In step 3), the synthesis route of the self-curing epoxy resin capable of multiple self-repairing is: 。 4. The water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating according to claim 2 or 3, characterized in that: In step 3.1), the molar ratio of (2-aminoethyl)ethylcarbamate to maleic anhydride is 1:(1-1.2); the molar ratio of furfurylamine to di-tert-butyl dicarbonate is 1:(2-2.1); and the molar ratio of maleimide monomer to furan monomer is 1:(1-1.1).

5. The water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating according to claim 4, characterized in that: Step 3.1) includes the following steps: 3.1.1) Dissolve tert-butyl (2-aminoethyl)ethylcarbamate in dichloromethane, add maleic anhydride, then add acetone, acetic anhydride, triethylamine and nickel acetate tetrahydrate, react at room temperature to 100°C for 1-5 hours, separate, wash and purify to obtain a maleimide monomer partially protected by a Boc group; wherein the molar ratio of tert-butyl (2-aminoethyl)ethylcarbamate, maleic anhydride and nickel acetate tetrahydrate is 1:(1-1.2):(0.9-1.1); 3.1.2) Dissolve furfurylamine in dichloromethane, add di-tert-butyl dicarbonate, react at room temperature to 80°C for 1-3 hours, separate, wash and purify to obtain a furan monomer partially protected by a Boc group; wherein the molar ratio of furfurylamine to di-tert-butyl dicarbonate is 1:(2-2.2); 3.1.3) The maleimide monomer obtained in step 1) and the furan monomer obtained in step 2) are dissolved in ethyl acetate, reacted at room temperature to 100°C for 1-12 hours, separated, washed and purified to obtain a DA cross-linking agent; wherein the molar ratio of the maleimide monomer to the furan monomer is 1:(1-1.2).

6. The water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating according to claim 2 or 3, characterized in that: In step 3.2), the molar ratio of hydroxyterephthalic acid to epichlorohydrin is 1:(1.1~1.2).

7. The water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating according to claim 6, characterized in that: Step 3.2) is to mix p-hydroxyterephthalic acid, excess epichlorohydrin and tetrabutylammonium iodide, stir and react at 80-150° C. for 1-12 hours, slowly dropwise add excess 1 mol / L sodium hydroxide solution, wash, distill at atmospheric pressure, extract and purify to obtain self-curable DHTA-ECH epoxy resin.

8. The water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating according to claim 2 or 3, characterized in that: In step 3.3), the mass ratio of DA crosslinker to self-curable DHTA-ECH epoxy resin is 1:(2~2.2).

9. The water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating according to claim 8, characterized in that: Step 3.3) is to mix the DA crosslinker with the self-curable DHTA-ECH epoxy resin at room temperature, degas in vacuum, and then stir and react at 50-80°C for 1-5 hours to obtain the DA-EP epoxy resin; wherein the mass ratio of the DA crosslinker to the self-curable DHTA-ECH epoxy resin is 1:(2~2.2).

10. The method for preparing the water-based intelligent corrosion inhibition-self-repairing anticorrosion composite coating according to any one of claims 1 to 9, characterized in that: After the water-based resin and the hollow fiber with a polymer cross-linked network structure are evenly mixed, a coating machine is used to spin-coat them on a metal substrate, and they are cured for 30 minutes to 24 hours at room temperature to 100°C to obtain a water-based intelligent corrosion inhibition-self-repairing anti-corrosion composite coating.

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