CN114634746A - 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 PDFInfo
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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 fluorescent warning and corrosion inhibition self-repairing functions are integrated through the composite molecular probe, so that coating components are reduced, and the coating complexity 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 with the functions of corrosion inhibition self-repairing and corrosion fluorescence warning; the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecule is applied to a coating and has double effects of damage self-warning and self-repairing.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a fluorescent self-warning, corrosion-inhibition 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 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 repair and autonomous repair. 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 that serve as warning or corrosion inhibitors that serve as repair can be caused by undesirable 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 is disclosed, in which a layer-by-layer self-assembly technology is used 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, the coating mode cannot timely give out a corrosion warning signal and effectively inhibit the corrosion activity in the actual use process.
Disclosure of Invention
The invention aims to provide a fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating, which integrates the functions of fluorescent warning and corrosion-inhibition self-repairing through a composite molecular probe, reduces coating components and reduces the complexity of the coating.
In order to solve the technical problems, the technical scheme adopted by the invention is that the fluorescent self-warning, corrosion-inhibition and 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 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 coating 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 aims to solve another technical problem of providing a preparation method of a fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating, which comprises the following steps:
s1 preparation of the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe: dropwise adding phosphorus oxychloride into dichloromethane in which basic rhodamine B is dissolved, 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 preparation of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules: in N2Eliminating 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 enable the rhodamine benzothiazole corrosion inhibition fluorescence composite molecular probe aqueous solution to generate self-assembly reaction; after complete reaction, obtaining the hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecule by centrifugation, washing and drying;
s3 preparation of the 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 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 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 N2Stirring 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 (4) dropwise adding the rhodamine benzothiazole corrosion inhibition fluorescence composite molecular probe aqueous solution obtained in the step S1 into the colloid suspension under the condition of continuous stirring, wherein the pH value is 10.
As a preferred embodiment of the present invention, in step S3: the stirring speed was 2000 and 3000 rpm.
Drawings
The following further 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 spectrum (contrast diagram) of hydrotalcite precursor and hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibiting 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 a cross-shaped scratch as photographed by a fluorescent metallographic microscope (in the figure, the light-colored portion is orange-red fluorescence);
fig. 4 shows electrochemical impedance spectroscopy of doped (inventive example 1) and undoped supramolecular artificial scratch damage coatings immersed in 3.5% NaCl solution for different time periods.
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 preparation of the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe: dropwise adding phosphorus oxychloride into dichloromethane dissolved in basic rhodamine B, and obtaining 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 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 hydrotalcite negativePreparing the rhodamine benzothiazole-loaded corrosion-inhibition fluorescent composite molecular probe supermolecule: in N2Under 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 fluorescence 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 preparation of the 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 hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecule suspension 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-inhibition 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, the solvent was evaporated to give 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 N2Stirring 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 (4) dropwise adding the rhodamine benzothiazole corrosion inhibition fluorescence composite molecular probe aqueous solution obtained in the step S1 into the colloid suspension under the condition of continuous stirring, wherein the pH value is 10.
In the step S3: the stirring speed was 2000-3000 rpm.
Specifically, the detailed description of the preparation method is made by the following three examples:
example 1:
s1 preparation of the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe: dissolving 5.00g of basic 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 as shown in figure 1; s2 preparation of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules: 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; at N2Dropping the mixed solution into 100mL of aqueous solution containing 12.75g of sodium nitrate under the atmosphere, adjusting the pH value to be within 10 +/-0.5 by using sodium hydroxide solution in the dropping process, reacting for 2 hours, transferring the obtained white suspension into a stainless steel high-pressure reaction kettle, and controlling the temperature to be 65 DEG CAnd standing under vacuum for 24 hours; 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 N2Stirring 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 the transparent colloidal suspension of the hydrotalcite precursor 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, wherein the hydrotalcite-loaded rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe supramolecules are shown in figure 2;
s3 preparation of the 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 fluorescent composite molecular probe supermolecule obtained in the step S2 and 10g of water, stirring at 2000rmp of rotation speed for 1.5 hours, 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 at 3000rpm of rotation speed for 1.5 hours; obtaining the supermolecule-doped fluorescent self-warning and corrosion-inhibition self-repairing nano anticorrosive coating.
Example 2:
preparing a S1 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 chloride in 30mL 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 for three times by using 30mL of dichloromethane, and drying and filtering the organic layer to obtain the rhodamine benzothiazole corrosion inhibition fluorescent composite molecular probe;
s2 hydrotalcite supported hydrotalcitePreparing danmin benzothiazole corrosion-inhibition fluorescent composite molecular probe supermolecule: weighing 14.8g of zinc nitrate hexahydrate and 9.3g of aluminum nitrate nonahydrate, and dissolving in 100mL of deionized water to obtain a mixed solution; in N2Under 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 N2Stirring for 24 hours under the atmosphere to obtain transparent colloidal suspension; then, dropwise adding 0.002mol/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 supramolecule;
s3 preparation of the 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:
preparing a S1 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 preparation of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules: 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 N2Under 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 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; 0.05g of hydrotalcite precursor was dispersed in 50mL of formamide and sonicated for 1 hour in N2Stirring for 24 hours under the atmosphere to obtain 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 supramolecule;
s3 preparation of the 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 force is tested according to the GB/T1720-1979 standard; impact resistance was tested according to 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 | Example 3 |
| Efficiency of impedance repair (%) | 97 | 96 | 95 |
| Adhesion force | 8.5Mpa | 7.9Mpa | 8.1Mpa |
| Impact resistance | 90cm | 75cm | 80cm |
| Flexibility of the film | 0.9mm | 0.8mm | 0.9mm |
| Resistance to 3% NaCl | 700 hours | 650 hours | 670 hours |
| Salt fog resistance | 2800 |
2500 hours | 2600 hours |
| Resistance to 10% H2SO4 | 890 hours | 800 hours | 800 hours |
| Resisting 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. The nano anticorrosive coating with self-warning fluorescence, corrosion inhibition and self-repairing functions 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.
2. The fluorescence self-warning, corrosion-inhibition and self-repair 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-inhibiting and self-repairing nano anticorrosive coating as claimed in claim 2, wherein the defoamer is a BYK-028 defoamer, the leveling agent is a BYK-346 leveling agent, the dispersant is a PE100 wetting dispersant, 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 preparation of the 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 with 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 preparation of hydrotalcite-loaded rhodamine benzothiazole corrosion-inhibition fluorescent composite molecular probe supramolecules: in N2Under 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 fluorescence 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 preparation of the 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 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-inhibition self-repairing nano anticorrosive coating.
5. The method for preparing the fluorescent self-warning, corrosion-inhibiting and self-repairing 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, evaporating the solvent to obtain 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-inhibiting and self-repairing 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 N2Stirring 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 (4) dropwise adding the rhodamine benzothiazole corrosion inhibition fluorescence composite molecular probe aqueous solution obtained in the step S1 into the colloid suspension under the condition of continuous stirring, wherein the pH value is 10.
7. The method for preparing the fluorescent self-warning, corrosion-inhibiting and self-repairing nano anticorrosive coating according to claim 4, wherein in the step S3: the stirring speed was 2000 and 3000 rpm.
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| CN117777820B (en) * | 2024-02-28 | 2024-05-31 | 太原理工大学 | Reversible self-early warning and self-repairing coating and preparation method thereof |
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