CN114634746B - Fluorescent self-warning, corrosion-inhibition and self-repairing nano anticorrosive coating and preparation method thereof - Google Patents

Fluorescent self-warning, corrosion-inhibition and self-repairing nano anticorrosive coating and preparation method thereof Download PDF

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CN114634746B
CN114634746B CN202210132654.4A CN202210132654A CN114634746B CN 114634746 B CN114634746 B CN 114634746B CN 202210132654 A CN202210132654 A CN 202210132654A CN 114634746 B CN114634746 B CN 114634746B
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benzothiazole
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CN114634746A (en
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丁锐
岳庆先
吕静
梁暄
王玉玉
祝冰倩
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Yantai University
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Abstract

The invention relates to a fluorescence self-warning and corrosion-inhibition self-repairing nano anticorrosive coating and a preparation method thereof, wherein the fluorescence self-warning and corrosion-inhibition self-repairing nano anticorrosive coating comprises 45-65 parts by weight of aqueous epoxy emulsion, 1-5 parts by weight of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecule and 10-15 parts by weight of water; the composite molecular probe integrates the functions of fluorescence warning and corrosion inhibition self-repairing, so that the components of the coating are reduced, and the complexity of the coating is reduced. The hydrotalcite-loaded rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe supermolecule is prepared from the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe, and the corrosion inhibition fluorescent composite molecular probe has the iron ion response of corrosion inhibition self-repairing and corrosion fluorescence warning functions; the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules are applied to coatings, and have double effects of damage self-warning and self-repairing.

Description

Fluorescent self-warning, corrosion-inhibition and self-repairing nano anticorrosive coating and preparation method thereof
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a fluorescent self-warning, corrosion-inhibiting and self-repairing nano anticorrosive coating and a preparation method thereof.
Background
The structural steel is an important material foundation for developing marine industry, and is a basic material with extremely large consumption and wide application range. The corrosion protection of the ocean engineering structural steel has very important and profound significance for the sustainable development of ocean blue economy. The anticorrosive coating is efficient, simple and direct, and is also the most widely applied corrosion protection measure for marine environment steel structures. The american society of corrosion engineers in international corrosion survey reports indicates that corrosion resistant coatings can save corrosion costs by 30%.
The reasons and processes for failure of organic corrosion resistant coatings are complex. When bond rupture or even local damage is caused by solvent evaporation, component compatibility, environmental and mechanical factors and the like, the shielding property of the coating is reduced, and the penetration of corrosive media accelerates the local corrosion at the coating/metal interface, so that the coating is rapidly stripped and failed finally. Therefore, the local damage of the organic anticorrosive coating is a main factor of the failure of the coating, and the timely discovery and repair of the local damage of the coating can obviously improve the anticorrosive performance and service life of the coating. Local damage of the coating is often micro-nano-scale and is difficult to find. Meanwhile, local corrosion is hidden under the coating, so that the corrosion condition is difficult to find and accurately position in time, and the corrosion condition is unconsciously and rapidly developed. When the degree of visibility is reached, it indicates that the corrosion is already extremely severe. Therefore, it is urgently required to find local damage of the coating and local corrosion of the metal at an early stage so as to maintain the material in time before the material suffers from severe corrosion and deterioration.
The self-warning coating is doped with the fluorescent probe, responds to the mechanical damage of the coating or the environmental change (metal ions, pH and the like) related to corrosion, and quickly feeds back the damage and corrosion state of the coating through a fluorescent signal to determine the corrosion active site in time. Self-healing coatings are coatings that repair damage to the coating and restore corrosion protection with little or no external intervention. Self-healing techniques include non-autonomous healing and autonomous healing. For the self-repairing, a repairing agent or a corrosion inhibitor and the like are mainly doped in the coating, and a stimulation signal of the self-repairing comes from water molecules or pH changes of local mechanical damage and local corrosion of the coating, so that the repairing agent or the corrosion inhibitor can be actively released under the condition of not applying external intervention, and the integrity or the functional characteristics of the coating can be automatically repaired. The failure of fluorescent probes, which serve as warning functions, or corrosion inhibitors, which serve as repair functions, can be caused by adverse interactions with other components of the coating. Therefore, it is usually necessary to encapsulate them with microcapsules or molecular containers to prevent the probe molecules or corrosion inhibitors from coming into direct contact with the coating matrix prematurely, and to utilize the response of the encapsulating container to factors such as mechanical damage to the coating, water molecules or pH to effect release of the fluorescent probe molecules or corrosion inhibitors. The synergy of the self-warning and self-repairing functions is complementary to the improvement of the comprehensive corrosion resistance of the coating. Through the cooperation of the self-warning and self-repairing functions, a corrosion warning signal can be sent out in time before the damage of the coating is manually repaired, and the corrosion activity is effectively inhibited.
In chinese patent document CN105440884A, a preparation and application of a self-repairing corrosion-resistant coating of a waterborne epoxy resin are disclosed, wherein a layer-by-layer self-assembly technology is utilized to prepare a corrosion inhibitor-loaded waterborne nano-silica material, and the prepared corrosion inhibitor-loaded nano-silica material is dispersed in the waterborne epoxy resin coating. However, in the actual use process, the coating mode cannot give a corrosion warning signal in time and effectively inhibit the corrosion activity.
Disclosure of Invention
The invention aims to provide a nano anticorrosive coating with fluorescence self-warning and corrosion-inhibition self-repairing functions, which integrates the functions of fluorescence warning and corrosion-inhibition self-repairing through a composite molecular probe, reduces the components of the coating and reduces the complexity of the coating.
In order to solve the technical problems, the technical scheme adopted by the invention is that the nano anticorrosive coating with fluorescence self-warning, corrosion inhibition and self-repairing comprises 45-65 parts by weight of aqueous epoxy emulsion, 1-5 parts by weight of hydrotalcite-loaded rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe supermolecules and 10-15 parts by weight of water.
The hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecule is prepared from the rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe, and the corrosion-inhibition fluorescent composite molecular probe has the corrosion-inhibition self-repairing and iron ion response corrosion fluorescent warning functions; the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecule is applied to a coating, has double effects of damage self-warning and self-repairing, takes iron ions which are corrosion products of steel as signals to initiate fluorescent warning, solves early warning or false warning of pH response fluorescence, integrates the functions of fluorescent warning and corrosion-inhibition self-repairing through the composite molecular probe, reduces coating components, and reduces coating complexity.
The existing self-warning-self-repairing function synergistic technology adopts a pH-responsive fluorescent probe. Although the local corrosion may cause the pH change, the correspondence between the coating and the corrosion environment is not strict, which may cause early or false alarm. In addition, the existing self-warning-self-repairing functional technology adopts a mode of respectively doping a warning component and a repairing component, so that a coating system is complicated, the difficulty of component proportion research and preparation process research is increased, the production and application cost is improved, and the long-acting corrosion resistance of the coating is weakened.
As a preferred technical scheme of the invention, the paint also comprises an auxiliary agent which mainly comprises 0.5-2 parts of a defoaming agent, 0.5-2 parts of a flatting agent, 0.5-2 parts of a dispersing agent and 15-25 parts of a curing agent.
As a preferable technical scheme of the invention, the defoaming agent is a BYK-028 defoaming agent, the leveling agent is a BYK-346 leveling agent, the dispersing agent is a PE100 wetting dispersing agent, and the curing agent is an aqueous amine curing agent.
The invention provides a preparation method of a nano anticorrosive coating with fluorescence self-warning, corrosion inhibition and self-repairing functions, which comprises the following steps:
preparing an S1 rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe: dropwise adding phosphorus oxychloride into dichloromethane dissolved in basic rhodamine B, and obtaining a transition product rhodamine acyl chloride after reflux reaction and drying; dropwise adding the acetonitrile solution of 2-aminobenzothiazole and triethylamine into the acetonitrile solution of rhodamine acyl chloride, and obtaining a viscous oily crude product after reflux reaction and drying;
extracting the viscous oily substance by using deionized water and dichloromethane to remove impurities; drying and filtering the organic layer to obtain a product rhodamine benzothiazole, namely the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe;
s2, preparing the supermolecule of the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe: in N 2 Eliminating the interference of carbon dioxide in the atmosphere, and dropwise adding zinc nitrate hexahydrate and aluminum nitrate nonahydrate solution into sodium nitrate solution to obtain mixed solution; adjusting the mixed solution to be alkaline so as to generate hydroxide; putting the mixed solution into a high-pressure reaction kettle, and completely reacting at 65 ℃, wherein the reaction environment is a vacuum environment so as to eliminate the interference of carbon dioxide; obtaining a hydrotalcite precursor after centrifugation, washing and drying;
carrying out ultrasonic stripping on the hydrotalcite precursor in a formamide solvent to obtain a single-layer hydrotalcite colloidal suspension; dripping the rhodamine benzothiazole corrosion inhibition fluorescence composite molecular probe aqueous solution obtained in the step S1 into the colloidal suspension to perform self-assembly reaction; after complete reaction, obtaining the hydrotalcite loaded rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe supermolecule by centrifugation, washing and drying;
s3, preparing a fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating: mixing 45-65 parts of aqueous epoxy emulsion, 1-5 parts of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules obtained in the step S2 and 10-15 parts of water, and stirring at a rotating speed for 1.5-2 hours to form a fully and uniformly mixed supramolecular aqueous epoxy emulsion dispersion system; adding 0.5-2 parts of defoaming agent, 0.5-2 parts of flatting agent, 0.5-2 parts of dispersing agent and 15-25 parts of curing agent, mixing and stirring for 1.5-2 hours to obtain the fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating.
The fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating obtained by the preparation method of the fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating realizes fluorescent warning and self-repairing of coating damage, has repairing efficiency of more than 95 percent, has excellent anticorrosive performance, can be used as a corrosion protection coating of an infrastructure steel structure, prolongs the service life of the infrastructure steel structure, and has economic value and social benefit.
As a preferred embodiment of the present invention, in the step S1:
after refluxing for 6-12 hours, evaporating the solvent to obtain rhodamine acyl chloride; after refluxing for 4-6 hours, the solvent was evaporated to give a viscous oil; the viscous oil was extracted three times with deionized water and dichloromethane.
As a preferred embodiment of the present invention, in the step S2:
in the process of dropwise adding zinc nitrate hexahydrate and aluminum nitrate nonahydrate solution into sodium nitrate solution, adjusting the pH value to be within the range of 10 +/-0.5 by using sodium hydroxide solution; after the mixed solution reacts for 2-3 hours, transferring the obtained white suspension mixed solution into a stainless steel high-pressure reaction kettle; standing at 65 deg.C under vacuum for 24 hr;
in the step of obtaining the hydrotalcite precursor after centrifugation, washing and drying, the hydrotalcite precursor is washed for 3 times by deionized water and absolute ethyl alcohol and then dried at the temperature of 45 ℃;
ultrasonic stripping for 1-1.5 hr, and dissolving the obtained suspension in N 2 Stirring for 24 hours under the atmosphere to obtain the colloidal suspension;
the manner of dripping the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe aqueous solution obtained in the step S1 into the colloidal suspension is as follows: and (2) dropwise adding the rhodamine benzothiazole corrosion inhibition fluorescence composite molecular probe aqueous solution obtained in the step (S1) into the colloidal suspension under the condition of continuous stirring, wherein the pH is =10.
As a preferred embodiment of the present invention, in the step S3: the stirring speed is 2000-3000rpm.
Drawings
The following detailed description of embodiments of the invention is made with reference to the accompanying drawings:
FIG. 1 is an infrared spectrum of the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe obtained in step S1 in example 1 of the present invention;
FIG. 2 is an X-ray diffraction spectrogram (contrast chart) of the hydrotalcite precursor and the hydrotalcite-supported rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules in step S2 in example 1 of the present invention;
FIG. 3 is a fluorescent warning picture of the damage of the coating of example 1 of the present invention to the cross-shaped scratch by a fluorescent metallographic microscope (in the picture, light-colored portions are orange-red fluorescent light);
FIG. 4 is an electrochemical impedance spectrum of doped (inventive example 1) and undoped supramolecular artificial scratch damage coatings soaked in 3.5% NaCl solution environment for various periods of time.
Detailed Description
The nano anticorrosive coating with fluorescence self-warning, corrosion inhibition and self-repairing comprises, by weight, 45-65 parts of aqueous epoxy emulsion, 1-5 parts of hydrotalcite-loaded rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe supermolecular suspension, 10-15 parts of water and 15-25 parts of aqueous amine curing agent; and the assistant mainly comprises 0.5-2 parts of defoaming agent, 0.5-2 parts of flatting agent and 0.5-2 parts of dispersant.
The defoaming agent is a BYK-028 defoaming agent, the flatting agent is a BYK-346 flatting agent, and the dispersing agent is a PE100 wetting dispersing agent.
The preparation method of the fluorescent self-warning, corrosion-inhibition and self-repairing nano anticorrosive coating comprises the following steps:
s1, preparing a rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe: dropwise adding phosphorus oxychloride into dichloromethane in which basic rhodamine B is dissolved, and carrying out reflux reaction and drying to obtain rhodamine acyl chloride; dropwise adding the acetonitrile solution of 2-aminobenzothiazole and triethylamine into the acetonitrile solution of rhodamine acyl chloride, and obtaining a viscous oily substance after reflux reaction and drying;
extracting the viscous oily substance by using deionized water and dichloromethane; drying and filtering the organic layer to obtain rhodamine benzothiazole, namely the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe;
s2, preparing the supermolecule of the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe: in N 2 Under the conditions of atmosphere and alkalinity, dropwise adding zinc nitrate hexahydrate and aluminum nitrate nonahydrate solution into sodium nitrate solution to obtain mixed solution; putting the mixed solution into a high-pressure reaction kettle, and completely reacting at 65 ℃ under vacuum conditions; obtaining a hydrotalcite precursor after centrifugation, washing and drying;
carrying out ultrasonic stripping on the hydrotalcite precursor in a formamide solvent to obtain a colloidal suspension; dripping the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe aqueous solution obtained in the step S1 into the colloidal suspension; after complete reaction, obtaining the hydrotalcite loaded rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe supermolecule by centrifugation, washing and drying;
s3, preparing a fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating: mixing 45-65 parts of aqueous epoxy emulsion (aqueous epoxy resin F0707 produced by Shenzhen Jitian chemical Co., ltd.), 1-5 parts of the suspension of the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecule obtained in the step S2 and 10-15 parts of water, and stirring at a rotating speed for 1.5-2 hours; adding 15-25 parts of curing agent, 0.5-2 parts of defoaming agent, 0.5-2 parts of flatting agent, 0.5-2 parts of dispersing agent and 15-25 parts of curing agent, mixing, and stirring for 1.5-2 hours to obtain the fluorescent self-warning and corrosion-inhibiting self-repairing nano anticorrosive coating.
In the step S1:
after refluxing for 6-12 hours, evaporating the solvent to obtain rhodamine acyl chloride; after refluxing for 4-6 hours, evaporating the solvent to obtain a viscous oil; the viscous oil was extracted three times with deionized water and dichloromethane.
In the step S2:
in the process of dropwise adding zinc nitrate hexahydrate and aluminum nitrate nonahydrate solution into sodium nitrate solution, adjusting the pH value to be within the range of 10 +/-0.5 by using sodium hydroxide solution; after the mixed solution reacts for 2-3 hours, transferring the obtained white suspension mixed solution into a stainless steel high-pressure reaction kettle; standing at 65 deg.C under vacuum for 24 hr;
in the step of obtaining the hydrotalcite precursor after centrifugation, washing and drying, the hydrotalcite precursor is washed for 3 times by deionized water and absolute ethyl alcohol and then dried at the temperature of 45 ℃;
the ultrasonic stripping treatment time is 1-1.5 hours, and the obtained suspension is placed in N 2 Stirring for 24 hours under the atmosphere to obtain the colloidal suspension;
the manner of dripping the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe aqueous solution obtained in the step S1 into the colloidal suspension is as follows: and (2) dropwise adding the rhodamine benzothiazole corrosion inhibition fluorescence composite molecular probe aqueous solution obtained in the step (S1) into the colloidal suspension under the condition of continuous stirring, wherein the pH =10.
In the step S3: the stirring speed is 2000-3000rpm.
Specifically, the preparation process is illustrated in detail by the following three examples:
example 1:
preparing an S1 rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe: 5.00g of baseDissolving rhodamine B in 10mL of dichloromethane, and then dropwise adding 5mL of phosphorus oxychloride; refluxing the mixed solution for 8 hours, and evaporating the solvent to obtain rhodamine acyl chloride; dissolving rhodamine chloride in 15mL of acetonitrile (solution A); 1.50g of 2-aminobenzothiazole and 5mL of triethylamine were dissolved in 25mL of acetonitrile (solution B). Dropwise adding the solution B into the solution A, refluxing the mixed solution for 4 hours, and evaporating the solvent to obtain a viscous oily substance; adding 20mL of deionized water into the viscous oily substance, and extracting with 20mL of dichloromethane for three times; drying and filtering the organic layer to obtain the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe shown in figure 1; s2, preparing the supermolecule of the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe: weighing 7.43g of zinc nitrate hexahydrate and 4.69g of aluminum nitrate nonahydrate, and dissolving the zinc nitrate hexahydrate and the aluminum nitrate nonahydrate in 50mL of deionized water to obtain a mixed solution; in N 2 Under the atmosphere, dropwise adding the mixed solution into 100mL of aqueous solution containing 12.75g of sodium nitrate, adjusting the pH value to be within the range of 10 +/-0.5 by using a sodium hydroxide solution in the dropwise adding process, reacting for 2 hours, transferring the obtained white suspension into a stainless steel high-pressure reaction kettle, and standing for 24 hours at the temperature of 65 ℃ under the vacuum condition; centrifuging the suspension, collecting a white product, washing the white product for 3 times by using deionized water and absolute ethyl alcohol, and drying the white product at the temperature of 45 ℃ to obtain a hydrotalcite precursor; dispersing 0.1g of hydrotalcite precursor in 100mL of formamide, and carrying out ultrasonic treatment for 1 hour; the resulting suspension is placed in N 2 Stirring for 24 hours under the atmosphere to obtain transparent colloidal suspension; then, adding 0.001mol/L deprotonated probe (the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe obtained in the step S1) aqueous solution (500mL, pH = 10) dropwise into a hydrotalcite precursor transparent colloidal suspension under the condition of continuous stirring, after reacting for 24 hours, collecting a flocculent product through centrifugation, washing and drying to obtain the hydrotalcite-loaded rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe supramolecules, as shown in FIG. 2;
s3, preparing a fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating: mixing 50g of aqueous epoxy emulsion, 2g of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescence composite molecular probe supermolecule obtained in the step S2 and 10g of water, stirring for 1.5 hours at the rotating speed of 2000rmp, adding 15g of ADEKA-15 aqueous amine curing agent, 0.5g of BYK-028 defoaming agent, 0.5g of BYK-346 flatting agent and 0.5g of PE100 wetting dispersant, and stirring for 1.5 hours at the rotating speed of 3000 rpm; obtaining the supermolecule-doped fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating.
Example 2:
s1, preparing a rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe: dissolving 10.00g of basic rhodamine B in 20mL of dichloromethane, and then dropwise adding 12mL of phosphorus oxychloride to obtain a mixed solution; refluxing the mixed solution for 12 hours, and evaporating the solvent to obtain rhodamine acyl chloride; dissolving rhodamine acyl chloride in 30mL of acetonitrile (solution A); dissolving 3.5g of 2-aminobenzothiazole and 10mL of triethylamine in 25mL of acetonitrile (solution B), dropwise adding the solution B into the solution A, refluxing for 6 hours, and evaporating the solvent to obtain a viscous oily substance; adding 30mL of deionized water into the viscous oily matter, extracting three times by using 30mL of dichloromethane, and drying and filtering an organic layer to obtain the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe;
preparing S2 hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules: weighing 14.8g of zinc nitrate hexahydrate and 9.3g of aluminum nitrate nonahydrate, and dissolving the zinc nitrate hexahydrate and the aluminum nitrate nonahydrate in 100mL of deionized water to obtain a mixed solution; at N 2 Under the atmosphere, dropwise adding the mixed solution into 200mL of aqueous solution containing 25.5g of sodium nitrate, adjusting the pH value to be within the range of 10 +/-0.5 by using a sodium hydroxide solution in the dropwise adding process, reacting for 3 hours, transferring the obtained white suspension into a stainless steel high-pressure reaction kettle, and standing for 24 hours at the temperature of 65 ℃ under the vacuum condition; centrifuging the suspension, collecting a white product, washing the white product for 3 times by using deionized water and absolute ethyl alcohol, and drying the white product at the temperature of 45 ℃ to obtain a hydrotalcite precursor; 0.2g of hydrotalcite precursor was dispersed in 200mL of formamide and sonicated for 1.5 hours in N 2 Stirring for 24 hours under the atmosphere to obtain transparent colloidal suspension; then, 0.002mol/L of deprotonated probe (the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe obtained in the step S1) water solution (500mL, pH = 10) is added into the hydrotalcite precursor transparent colloid suspension drop by drop under the condition of continuous stirring, and the reaction 24 is carried outAfter hours, collecting a flocculent product through centrifugation, washing and drying to obtain the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecule;
s3, preparing a nano anticorrosive coating with fluorescence self-warning, corrosion inhibition and self-repairing functions: mixing 100g of aqueous epoxy emulsion, 5g of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecule obtained in the step S2 and 20g of water, and stirring for 2 hours at the rotating speed of 2000 rmp; adding 30g of ADEKA-15 aqueous amine curing agent, 1g of BYK-028 defoaming agent, 1g of BYK-346 flatting agent and 1g of PE100 wetting dispersant, and stirring at 3000rpm for 2 hours to obtain the supramolecular doped fluorescence self-warning and corrosion-inhibition self-repairing nano anticorrosive coating.
Example 3:
s1, preparing a rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe: dissolving 2.50g of basic rhodamine B in 5mL of dichloromethane, then dropwise adding 2.0mL of phosphorus oxychloride to obtain a mixed solution, refluxing the mixed solution for 6 hours, and evaporating the solvent to obtain rhodamine acyl chloride; dissolving rhodamine acyl chloride in 8mL of acetonitrile (solution A), dissolving 0.6g of 2-aminobenzothiazole and 2.5mL of triethylamine in 12mL of acetonitrile (solution B), dropwise adding the solution B into the solution A, refluxing for 4 hours, and evaporating the solvent to obtain a viscous oily substance; adding 10mL of deionized water into the viscous oily matter, extracting for three times by using 15mL of dichloromethane, and drying and filtering the organic layer to obtain the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe;
s2, preparing the supermolecule of the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe: 3.70g of zinc nitrate hexahydrate and 2.35g of aluminum nitrate nonahydrate are weighed and dissolved in 25mL of deionized water to obtain a mixed solution; in N 2 Under the atmosphere, dropwise adding the mixed solution into 50mL of aqueous solution containing 6.40g of sodium nitrate, adjusting the pH value to be within the range of 10 +/-0.5 by using a sodium hydroxide solution in the dropwise adding process, reacting for 2 hours, transferring the obtained white suspension into a stainless steel high-pressure reaction kettle, and standing for 24 hours at the temperature of 65 ℃ under the vacuum condition; centrifuging the suspension, collecting white product, washing with deionized water and anhydrous ethanol for 3 times, and drying at 45 deg.C to obtain hydrotalcite precursor(ii) a 0.05g of hydrotalcite precursor was dispersed in 50mL of formamide and sonicated for 1 hour in N 2 Stirring for 24 hours under the atmosphere to obtain a transparent colloidal suspension; then, dropwise adding 0.0005mol/L deprotonated probe (the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe obtained in the step S1) aqueous solution (500mL, pH = 10) into a transparent colloidal suspension of a hydrotalcite precursor under the condition of continuous stirring, after reacting for 24 hours, centrifugally collecting a flocculent product, washing and drying to obtain the hydrotalcite-loaded rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe supramolecules;
s3, preparing a fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating: mixing 25g of aqueous epoxy emulsion, 0.8g of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecule and 5g of water, and stirring for 1.5 hours at the rotating speed of 2000 rmp; adding 8g of ADEKA-15 aqueous amine curing agent, 0.25g of BYK-028 defoaming agent, 0.25g of BYK-346 flatting agent and 0.25g of PE100 wetting dispersant, and stirring at the rotating speed of 3000rpm for 1.5 hours to obtain the supermolecule-doped fluorescence self-warning and corrosion-inhibition self-repairing nano anticorrosive coating.
The fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating obtained in the embodiment 1-3 is tested by using a fluorescent microscope to test the damage warning performance of the coating adopting the mixture; testing the impedance repairing efficiency before and after the coating is repaired by utilizing an electrochemical alternating current impedance spectrum technology; the adhesion is tested according to the GB/T1720-1979 standard; the impact resistance is tested according to the GB/T1732-1993 standard; flexibility is tested according to GB/T1720-79 standard; the salt water resistance is tested according to the GB/T1763-89 standard; the salt spray resistance is tested according to the GB/T1771-91 standard; the acid and alkali resistance is tested according to the GB/T1763 standard; the humidity and heat resistance is tested according to the GB/T1740 standard; the data from the specific tests are shown in table 1 below.
TABLE 1 fluorescence self-warning and corrosion-inhibition self-repairing nano-anticorrosion coating test data
Item Example 1 Example 2 Embodiment 3
Efficiency of impedance repair (%) 97 96 95
Adhesion force 8.5Mpa 7.9Mpa 8.1Mpa
Impact resistance 90cm 75cm 80cm
Flexibility 0.9mm 0.8mm 0.9mm
Resistance to 3% NaCl 700 hours 650 hours 670 hours
Salt fog resistance 2800 hours 2500 hours 2600 hours
Tolerance to 10% H 2 SO 4 890 hours 800 hours 800 hours
Tolerance to 10% NaOH 850 hours 780 hours 800 hours
From the data, the fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating realizes fluorescent warning (figure 3) and self-repairing of coating damage, the repairing efficiency reaches more than 95% (figure 4), the coating has excellent anticorrosive performance, can be used as a corrosion protection coating of an infrastructure steel structure, prolongs the service life of the infrastructure steel structure, and has economic value and social benefit.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like, such as changes in shape or material of some components, may be made within the spirit and principle of the present invention; are intended to be included within the scope of the present invention.

Claims (7)

1. A fluorescence self-warning and corrosion-inhibition self-repairing nano anticorrosive coating is characterized by comprising 45-65 parts by weight of aqueous epoxy emulsion, 1-5 parts by weight of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecules and 10-15 parts by weight of water;
the preparation method of the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecule comprises the following steps: s1, preparing a rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe: dropwise adding phosphorus oxychloride into dichloromethane in which basic rhodamine B is dissolved, and carrying out reflux reaction and drying to obtain rhodamine acyl chloride; dropwise adding the acetonitrile solution of 2-aminobenzothiazole and triethylamine into the acetonitrile solution of rhodamine acyl chloride, and obtaining a viscous oily substance after reflux reaction and drying;
extracting the viscous oily substance by using deionized water and dichloromethane; drying and filtering the organic layer to obtain rhodamine benzothiazole, namely the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe;
s2, preparing the supermolecule of the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe: at N 2 Under the conditions of atmosphere and alkalinity, dropwise adding zinc nitrate hexahydrate and aluminum nitrate nonahydrate solution into sodium nitrate solution to obtain mixed solution; then placing the mixed solution into a high-pressure reaction kettle, and completely reacting at 65 ℃ under vacuum conditions; obtaining a hydrotalcite precursor after centrifugation, washing and drying;
carrying out ultrasonic stripping on the hydrotalcite precursor in a formamide solvent to obtain a colloidal suspension; dripping the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe aqueous solution obtained in the step S1 into the colloidal suspension; after complete reaction, obtaining the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecule by centrifugation, washing and drying.
2. The fluorescence self-warning, corrosion-inhibiting and self-repairing nano anticorrosive coating as claimed in claim 1, further comprising an auxiliary agent mainly comprising 0.5-2 parts of a defoaming agent, 0.5-2 parts of a leveling agent, 0.5-2 parts of a dispersing agent and 15-25 parts of a curing agent.
3. The fluorescence self-warning, corrosion-inhibition and self-repair nano anticorrosive coating as claimed in claim 2, wherein the defoaming agent is a BYK-028 defoaming agent, the leveling agent is a BYK-346 leveling agent, the dispersing agent is a PE100 wetting dispersing agent, and the curing agent is a water-based amine curing agent.
4. The preparation method of the fluorescent self-warning, corrosion-inhibition and self-repairing nano anticorrosive coating as claimed in claim 1, characterized by comprising the following steps:
s1, preparing a rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe: dropwise adding phosphorus oxychloride into dichloromethane in which basic rhodamine B is dissolved, and carrying out reflux reaction and drying to obtain rhodamine acyl chloride; dropwise adding the acetonitrile solution of 2-aminobenzothiazole and triethylamine into the acetonitrile solution of rhodamine acyl chloride, and obtaining a sticky oily substance after reflux reaction and drying;
extracting the viscous oily substance by using deionized water and dichloromethane; drying and filtering the organic layer to obtain rhodamine benzothiazole, namely the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe;
preparing S2 hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules: in N 2 Under the conditions of atmosphere and alkalinity, dropwise adding zinc nitrate hexahydrate and aluminum nitrate nonahydrate solution into sodium nitrate solution to obtain mixed solution; putting the mixed solution into a high-pressure reaction kettle, and completely reacting at 65 ℃ under vacuum conditions; obtaining a hydrotalcite precursor after centrifugation, washing and drying;
carrying out ultrasonic stripping on the hydrotalcite precursor in a formamide solvent to obtain a colloidal suspension; dropwise adding the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe aqueous solution obtained in the step S1 into the colloidal suspension; after complete reaction, obtaining the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecule by centrifugation, washing and drying;
s3, preparing a fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating: mixing 45-65 parts of aqueous epoxy emulsion, 1-5 parts of the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules obtained in the step S2 and 10-15 parts of water, and stirring for 1.5-2 hours; adding 0.5-2 parts of defoaming agent, 0.5-2 parts of flatting agent, 0.5-2 parts of dispersing agent and 15-25 parts of curing agent, mixing and stirring for 1.5-2 hours to obtain the fluorescent self-warning and corrosion-inhibiting self-repairing nano anticorrosive coating.
5. The method for preparing the fluorescent self-warning, corrosion-inhibition and self-repair nano anticorrosive coating according to claim 4, wherein in the step S1:
after refluxing for 6-12 hours, evaporating the solvent to obtain rhodamine acyl chloride; after refluxing for 4-6 hours, the solvent was evaporated to give a viscous oil; the viscous oil was extracted three times with deionized water and dichloromethane.
6. The method for preparing the fluorescent self-warning, corrosion-inhibition and self-repair nano anticorrosive coating according to claim 4, wherein in the step S2:
in the process of dropwise adding zinc nitrate hexahydrate and aluminum nitrate nonahydrate solution into sodium nitrate solution, adjusting the pH value to be within the range of 10 +/-0.5 by using sodium hydroxide solution; after the mixed solution reacts for 2-3 hours, transferring the obtained white suspension mixed solution into a stainless steel high-pressure reaction kettle; standing at 65 deg.C under vacuum for 24 hr;
in the step of obtaining the hydrotalcite precursor after centrifugation, washing and drying, the hydrotalcite precursor is washed for 3 times by deionized water and absolute ethyl alcohol and then dried at the temperature of 45 ℃;
the ultrasonic stripping treatment time is 1-1.5 hours, and the obtained suspension is placed in N 2 Stirring for 24 hours under the atmosphere to obtain the colloidal suspension;
the manner of dripping the rhodamine benzothiazole corrosion inhibition fluorescence composite molecular probe aqueous solution obtained in the step S1 into the colloidal suspension is as follows: and (2) dropwise adding the rhodamine benzothiazole corrosion inhibition fluorescence composite molecular probe aqueous solution obtained in the step (S1) into the colloidal suspension under the condition of continuous stirring, wherein the pH is =10.
7. The method for preparing the fluorescent self-warning, corrosion-inhibition and self-repair nano anticorrosive coating according to claim 4, wherein in the step S3: the stirring speed is 2000-3000rpm.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105820283A (en) * 2016-06-13 2016-08-03 苏州吉人高新材料股份有限公司 Fluorescent latex containing rhodamine B and preparing method thereof
CN106994356A (en) * 2017-06-02 2017-08-01 南京工程学院 The preparation method of photochemical catalyst CdS NiS nano composite materials

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2309887C (en) * 1995-12-05 2002-02-12 Prestone Products Corporation Neoacid corrosion inhibitors
JP3851706B2 (en) * 1996-05-20 2006-11-29 日清紡績株式会社 Fluorescent group-containing carbodiimide compound
US7381516B2 (en) * 2002-10-02 2008-06-03 3M Innovative Properties Company Multiphoton photosensitization system
US20080076139A1 (en) * 2006-09-21 2008-03-27 Sharat Singh Methods and compositions for detecting the activation states of multiple signal transducers in rare circulating cells
CN105884788B (en) * 2016-05-13 2018-04-03 南京理工大学 A kind of Fe3+ molecular fluorescences sensor based on rhodamine B, preparation method and application
CN111098986B (en) * 2019-12-24 2021-07-13 烟台大学 Marine waste recovery device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105820283A (en) * 2016-06-13 2016-08-03 苏州吉人高新材料股份有限公司 Fluorescent latex containing rhodamine B and preparing method thereof
CN106994356A (en) * 2017-06-02 2017-08-01 南京工程学院 The preparation method of photochemical catalyst CdS NiS nano composite materials

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