CN113755001A - Poly (urea-carbamate)/polyaniline/graphene oxide composite self-healing anticorrosive material - Google Patents
Poly (urea-carbamate)/polyaniline/graphene oxide composite self-healing anticorrosive material Download PDFInfo
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Abstract
The invention discloses a poly (urea-carbamate)/polyaniline/graphene oxide composite self-healing anticorrosive material and a preparation method thereof, wherein the self-healing anticorrosive coating comprises a polyaniline/graphene oxide composite material and poly (urea-carbamate); the mass fraction of the polyaniline/graphene oxide composite material is 1% -3% of the total mass of the self-healing material. The self-healing anticorrosive paint prepared by the invention has simple preparation process, is easy to realize industrial production, and can be well applied to the field of intelligent anticorrosive coatings due to the specific self-healing capability and mechanical property.
Description
Technical Field
The invention relates to a self-healing intelligent anticorrosive coating, in particular to a poly (urea-carbamate)/polyaniline/graphene oxide composite self-healing anticorrosive material and a preparation method thereof.
Background
Inspired by the "passive injury-active repair" self-repair capability of living organisms, self-healing materials that can partially or completely recover the basic properties after mechanical damage are receiving increasing attention due to their potentially widespread use, such as sensors, wearable electronics, energy storage, biomedical engineering and functional coatings, especially in the field of anti-corrosive coatings. Unlike conventional anticorrosive coatings, self-healing materials that can repair internal defects in the coatings and spontaneously recover protective functions are considered as innovative technologies that can solve the increasingly serious corrosion problem worldwide and are of great significance. Maintenance costs can be reduced, service life extended and reliable protection provided for the base substrate.
Polyurethane coatings have unique corrosion, abrasion, and weather resistance characteristics and have been used in a variety of industrial applications. In the last decade, efforts have been made to impart self-healing functionality to coatings. One extrinsic approach to enhance the overall performance of a polyurethane anti-corrosive coating is to implant healing units (e.g., microcapsules or delivery systems) into the polyurethane anti-corrosive coating, wherein the pre-embedded active agent undergoes in situ polymerization by contact with a catalyst, thereby creating a compensatory network of glue in the damaged area and maintaining the integrity of the anti-corrosive coating. Although researchers have witnessed the rapid development of this constructive strategy in recent years, disadvantages inherent to the limited healing time or complex preparation procedures are inevitable. Typical inherently self-healing polyurethane materials mostly require input of external energy, such as heat, ultraviolet rays, etc., to facilitate reversible or exchange reactions. Anticorrosive coatings used in various environments are prone to microcracking due to incidental external forces that are difficult to detect without immediate remedial action and eventually propagate to macrocracks. It is difficult to grasp the appropriate time to apply the stimulus to initiate the self-healing process. Driven by practical demands, research has focused on the principles of supramolecular architecture. Although many room temperature self-healing supramolecular polymers have recently been constructed through the use of complex supramolecular motifs (e.g., hydrogen bonding, metal coordination bonds, host-guest interactions), most of them are mechanically poor materials that do not provide better hardness to the polyurethane corrosion protection coating to accommodate the service environment where complex tear and impact strength are a prerequisite. To date, it remains a challenge to prepare polyurethane anti-corrosive coatings having excellent mechanical strength, high fracture toughness, and inherent room temperature self-healing characteristics.
Disclosure of Invention
The invention aims to provide a poly (urea-carbamate)/polyaniline/graphene oxide composite self-healing anticorrosive material and a preparation method thereof.
A poly (urea-carbamate)/polyaniline/graphene oxide composite self-healing anticorrosive material and a preparation method thereof comprise the following steps:
(1) placing the hydrochloric acid solution of aniline in the graphene oxide turbid liquid, and stirring for 1-2 hours in an ice-water bath to obtain a stable mixed solution; continuously adding a hydrochloric acid solution of ammonium persulfate, stirring for 12-24 hours in an ice-water bath, standing, filtering, washing, and freeze-drying to obtain the polyaniline-graphene oxide composite material;
(2) dropwise adding an N, N-dimethylformamide solution of adipic dihydrazide into an N, N-dimethylformamide solution of toluene-2, 4-diisocyanate-terminated polypropylene glycol under stirring, reacting under stirring at 115-125 ℃ for 16-24 hours, adding an N, N-dimethylformamide dispersion solution of the polyaniline-graphene oxide composite material obtained in the step (1), stirring at normal temperature for 4-8 hours, and drying to obtain the poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material.
Preferably, in the step (1), the concentration of aniline in the hydrochloric acid solution of aniline is 0.2 mol/l, and the concentration of hydrogen chloride is 0.2 mol/l; the concentration of ammonium persulfate in the hydrochloric acid solution of ammonium persulfate was 0.13 mol/liter, and the concentration of hydrogen chloride was 0.2 mol/liter.
Preferably, in the step (1), the mass ratio of aniline to graphene oxide is 10-20: 1; the molar ratio of hydrogen chloride to aniline in the hydrochloric acid solution of aniline is 0.5-1.5: 1; the molar ratio of ammonium persulfate to aniline is 0.5-2: 1.
Preferably, in the step (1), the mass ratio of the graphene oxide to the water in the graphene oxide suspension is 0.0005-0.002: 1.
Preferably, in the step (2), the mass concentration of the toluene-2, 4-diisocyanate terminated polypropylene glycol in the N, N-dimethylformamide solution of the toluene-2, 4-diisocyanate terminated polypropylene glycol is 9 to 15%, the mass concentration of the adipic acid dihydrazide in the N, N-dimethylformamide solution of the adipic acid dihydrazide is 0.6 to 1.1%, and the mass ratio of the toluene-2, 4-diisocyanate terminated polypropylene glycol to the adipic acid dihydrazide is 14.25 to 14.5: 1.
Preferably, in the step (2), the temperature of the N, N-dimethylformamide solution of the toluene-2, 4-diisocyanate terminated polypropylene glycol is 45-60 ℃; the temperature of the N, N-dimethylformamide solution of adipic dihydrazide is 100-120 ℃.
Preferably, in the step (2), the mass ratio of the polyaniline-graphene oxide composite material to the toluene-2, 4-diisocyanate-terminated polypropylene glycol is 1:46, and the mass ratio of the toluene-2, 4-diisocyanate-terminated polypropylene glycol to the adipic acid dihydrazide is 57.5: 4.
Compared with the prior art, the invention has the beneficial effects that:
(1) the poly (urea-urethane) chain in the composite material prepared by the invention is rich in urea, and a plurality of hydrogen bonds of urethane and amide groups enable the poly (urea-urethane)/polyaniline/graphene oxide composite material to have a self-repairing function at room temperature.
(2) Compared with the original poly (urea-urethane) coating, the composite material prepared by the invention takes polyaniline/graphene oxide as rigid nano filler, so that the hardness of the coating is qualified, and the interface hydrogen bond between the polyaniline/graphene oxide and the poly (urea-urethane) matrix is used as a reversible sacrificial bond, so that the tensile strength and toughness of the composite material are greatly improved, and the tearing strength and impact strength of the coating are improved.
(3) The laminar polyaniline/graphene oxide in the composite material prepared by the method has the effect of blocking the penetration of aggressive substances, and the penetration resistance of the coating is improved, so that the corrosion resistance of the coating is improved.
Drawings
Fig. 1 is a scanning electron microscope image of polyaniline/graphene oxide prepared by the present invention.
Fig. 2 is a fourier transform infrared spectrum of graphene oxide and polyaniline/graphene oxide prepared by the present invention.
FIG. 3 is an electrochemical impedance spectrum of the coatings of examples 1-3 of the present invention and comparative examples 1-3.
Fig. 4 is a stress-strain graph of inventive example 1 and comparative example 1.
FIG. 5 is a graph of the stress-strain curves of the material of example 1 of the present invention after uncut and shear healing.
Detailed Description
The invention is further elucidated with reference to the figures and embodiments.
The poly (urea-carbamate)/polyaniline/graphene oxide composite self-healing anticorrosive material and the preparation method thereof comprise the following steps:
(1) adding graphene oxide into deionized water, and performing ultrasonic dispersion for 1-2 hours to obtain a graphene oxide suspension, wherein the mass ratio of the graphene oxide to the deionized water is 0.0005-0.002: 1; then, adding an aniline monomer into a 0.2 mol/L hydrogen chloride solution, magnetically stirring, adding the aniline monomer into a graphene oxide suspension, and magnetically stirring for 1-2 hours in an ice-water bath to obtain a stable mixed solution, wherein the mol ratio of hydrogen chloride to aniline is 0.5-1.5: 1, and the mass ratio of aniline to graphene oxide is 10-20: 1; and adding ammonium persulfate into 0.2 mol/L hydrogen chloride solution, wherein the mol ratio of hydrogen chloride to ammonium persulfate is 1-2: 1, adding the mixture into the mixed solution, wherein the mol ratio of ammonium persulfate to aniline is 0.5-2: 1, magnetically stirring for 12-24 hours in an ice water bath, standing, filtering, washing, and freeze-drying to obtain the polyaniline/graphene oxide composite material.
(2) Dissolving toluene-2, 4-diisocyanate-terminated polypropylene glycol into N, N-dimethylformamide at the ambient temperature of 45-60 ℃, wherein the mass ratio of the toluene-2, 4-diisocyanate-terminated polypropylene glycol to the N, N-dimethylformamide is 0.09-0.15: 1; then dissolving adipic acid dihydrazide in N, N-dimethylformamide at 100-120 ℃, wherein the mass ratio of the adipic acid dihydrazide to the N, N-dimethylformamide is 0.006-0.011: 1, and the mass ratio of toluene-2, 4-diisocyanate-terminated polypropylene glycol to the adipic acid dihydrazide is 14.25-14.5: 1, dropwise adding the obtained solution into the toluene-2, 4-diisocyanate-terminated polypropylene glycol solution under stirring, and then magnetically stirring the mixed solution at the temperature of 115-125 ℃ for 16-24 hours; and (2) dissolving the polyaniline/graphene oxide obtained in the step (1) in N, N-dimethylformamide, ultrasonically dispersing for 1-2 hours, adding into the mixed solution, wherein the mass ratio of the mass of the polyaniline/graphene oxide to the total solute (including toluene-2, 4-diisocyanate-terminated polypropylene glycol, adipic dihydrazide and polyaniline/graphene oxide) is 0.01-0.03: 1, stirring at normal temperature for 4-8 hours, and drying to obtain the poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material.
Example 1
(1) Dispersing 0.5 g of graphene oxide in 1 liter of deionized water, and carrying out ultrasonic treatment for 2 hours to obtain a stable graphene oxide suspension; dissolving 10 ml of aniline in 0.5L of 0.2 mol/L hydrochloric acid solution, magnetically stirring to prepare aniline/hydrochloric acid solution, adding the aniline/hydrochloric acid solution into the graphene oxide suspension, and magnetically stirring for 1 hour in ice water bath to obtain stable mixed solution; and dissolving 30.5 g of ammonium persulfate in 1L of 0.2 mol/L hydrochloric acid solution, adding the solution into the mixed solution, magnetically stirring the solution for 24 hours in an ice-water bath, standing, filtering, washing and freeze-drying the solution to obtain the polyaniline/graphene oxide composite material.
(2) 2.3g of toluene-2, 4-diisocyanate-terminated polypropylene glycol (commercially available, Sigma-Aldrich reagent) were dissolved in 20 ml of N, N-dimethylformamide at 50 ℃ at ambient temperature; then, 0.16g of adipic acid dihydrazide (commercially available, J & K Chemicals halocarb chemical) was completely dissolved in 20 ml of hot N, N-dimethylformamide (120 ℃ C.), and the resultant solution was dropwise added to the above toluene-2, 4-diisocyanate-terminated polypropylene glycol solution with stirring, followed by magnetically stirring the mixed solution at a temperature of 120 ℃ for 16 hours; and (2) dissolving 0.05g of polyaniline/graphene oxide obtained in the step (1) in N, N-dimethylformamide, ultrasonically dispersing for 1 hour, adding into the mixed solution, stirring at normal temperature for 4 hours, and drying to obtain the poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material, wherein the mass of the polyaniline/graphene oxide is 2% of that of the self-healing material.
In the poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material obtained in this embodiment, the mass percentage of polyaniline/graphene oxide is 2%. As shown in fig. 1, which is a scanning electron microscope image of polyaniline/graphene oxide prepared by the present invention, polyaniline/graphene oxide has a rough surface, and polyaniline is uniformly dispersed in the polyaniline layer and between the polyaniline layer, because the graphene oxide structure with a large specific surface area contains strong hydrophilic functional groups such as ether bond, carbonyl group, carboxyl group, etc., so that aniline after mixing is easily adsorbed on the surface of graphene oxide, and forms a spherical structure through oxidative polymerization.
FIG. 2 shows a Fourier transform infrared spectrogram of graphene oxide and polyaniline/graphene oxide prepared by the method, and an infrared spectrum 1715cm of graphene oxide-1Peak at 1614cm, C = O stretching vibration in carboxylic acid and carbonyl group-1The peak is 1031cm of ring skeleton vibration peak of graphene oxide-1The peak is the C-O-C stretching vibration of the epoxide on the surface of the graphene oxide, and the peak is 971cm-1The peak at (a) is the carboxyl C-OH stretching vibration, and the above characterization provides evidence of the presence of hydroxyl, carboxyl, ring backbone and epoxy groups in graphene oxide. Infrared spectrum 1297 cm of polyaniline-graphene oxide-1And (c) 1241cm-1The peak values of the points respectively correspond to N-H bending vibration characteristic peaks, 822cm, corresponding to aromatic secondary amine in polyaniline/graphene oxide-1The peak corresponds to the absorption peak of the out-of-plane bending deformation of C-H on the polyaniline benzene ring, so that the success of polyaniline grafted graphene oxide can be seen.
As shown in fig. 3, which is an electrochemical impedance spectrum of the coatings of examples 1 to 3 and comparative examples 1 to 3, it can be seen that the electrochemical impedance value is the highest when the mass percentage of polyaniline/graphene oxide is 2%.
As shown in fig. 4, which is a stress-strain curve diagram of example 1 and comparative example 1, it can be seen that polyaniline/graphene oxide as a reinforcing material improves the tensile strength of the self-healing anticorrosive material by 3.35 times, but does not improve the elongation at break.
As shown in fig. 5, which is a stress-strain curve diagram of the material of example 1 after being uncut and being cut and healed, the uncut poly (urea-urethane)/polyaniline/graphene oxide sample has better mechanical tensile property, and in the process of practical experiment, we find that after the cut two-part section is pushed together and kept for 1 minute, the two parts are reconnected, the healed joint can be freely bent, and the strength is enough to bear a certain tensile force. The tensile strength and the elongation at break of the sample strips are also obviously increased along with the increase of the healing time, and after the healing time is 48 hours, the tensile strength of the sample reaches about 4.17MPa, the elongation at break is about 723.0%, and the tensile strength and the elongation at break reach 88.35% and 84.97% respectively when the sample is not sheared, and the healing effect is good.
Example 2
(1) Dispersing 2g of graphene oxide in 1L of deionized water, and performing ultrasonic treatment for 1 hour to obtain a stable graphene oxide suspension; dissolving 20 ml of aniline in 1L of 0.2 mol/L hydrochloric acid solution, magnetically stirring to prepare aniline/hydrochloric acid solution, adding the aniline/hydrochloric acid solution into the graphene oxide suspension, and magnetically stirring for 2 hours in ice water bath to obtain stable mixed solution; and dissolving 23 g of ammonium persulfate in 0.5L of 0.2 mol/L hydrochloric acid solution, adding the solution into the mixed solution, magnetically stirring the solution in an ice-water bath for 12 hours, standing, filtering, washing and freeze-drying the solution to obtain the polyaniline/graphene oxide composite material.
(2) 1.8g of toluene-2, 4-diisocyanate-terminated polypropylene glycol was dissolved in 20 ml of N, N-dimethylformamide at 60 ℃ at ambient temperature; then, 0.125g of adipic acid dihydrazide was completely dissolved in 20 ml of hot N, N-dimethylformamide (100 ℃ C.), and the resultant solution was dropwise added to the above toluene-2, 4-diisocyanate-terminated polypropylene glycol solution with stirring, followed by magnetically stirring the mixed solution at 125 ℃ for 24 hours; and (2) dissolving 0.058g of polyaniline/graphene oxide obtained in the step (1) in N, N-dimethylformamide, ultrasonically dispersing for 2 hours, adding into the mixed solution, stirring at normal temperature for 8 hours, and drying to obtain the poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material, wherein the mass of the polyaniline/graphene oxide is 3% of that of the self-healing material.
In the poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material obtained in this embodiment, the mass percentage of polyaniline/graphene oxide is 3%. As shown in fig. 3, when the mass percentage of polyaniline/graphene oxide is 3%, the electrochemical resistance value is slightly lower than that of example 1.
Example 3
(1) Dispersing 1.5 g of graphene oxide in 1 liter of deionized water, and carrying out ultrasonic treatment for 1.5 hours to obtain a stable graphene oxide suspension; dissolving 16 ml of aniline in 0.8L of 0.2 mol/L hydrochloric acid solution, magnetically stirring to prepare aniline/hydrochloric acid solution, adding the aniline/hydrochloric acid solution into the graphene oxide suspension, and magnetically stirring for 1 hour in ice water bath to obtain stable mixed solution; and dissolving 20 g of ammonium persulfate in 0.8L of 0.2 mol/L hydrochloric acid solution, adding into the mixed solution, magnetically stirring for 18 hours in an ice-water bath, standing, filtering, washing, and freeze-drying to obtain the polyaniline/graphene oxide composite material.
(2) 3g of toluene-2, 4-diisocyanate-terminated polypropylene glycol was dissolved in 20 ml of N, N-dimethylformamide at 45 ℃ at ambient temperature; then, 0.21g of adipic acid dihydrazide was completely dissolved in 20 ml of hot N, N-dimethylformamide (110 ℃ C.), and the resultant solution was dropwise added to the above toluene-2, 4-diisocyanate-terminated polypropylene glycol solution with stirring, followed by magnetically stirring the mixed solution at a temperature of 115 ℃ for 18 hours; and (2) subsequently, dissolving 0.032g of polyaniline/graphene oxide obtained in the step (1) in N, N-dimethylformamide, ultrasonically dispersing for 1.5 hours, adding into the mixed solution, stirring at normal temperature for 6 hours, and drying to obtain the poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material, wherein the mass of the polyaniline/graphene oxide is 1% of that of the self-healing material.
In the poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material obtained in this embodiment, the mass percentage of polyaniline/graphene oxide is 1%. As shown in fig. 3, when the mass percentage of polyaniline/graphene oxide is 1%, the electrochemical resistance value is lower than that of examples 1 and 2.
Comparative example 1
In comparative example 1, the preparation steps of the polyaniline/graphene oxide composite material in example 1 are eliminated, and the other steps are the same as those in example 1, and the specific operations are as follows:
2.3g of toluene-2, 4-diisocyanate-terminated polypropylene glycol are dissolved in 20 ml of N, N-dimethylformamide at 50 ℃ at ambient temperature; then, 0.16g of adipic acid dihydrazide was completely dissolved in 20 ml of hot N, N-dimethylformamide (120 ℃ C.), and the resultant solution was dropwise added to the above toluene-2, 4-diisocyanate-terminated polypropylene glycol solution with stirring, followed by magnetically stirring the mixed solution at a temperature of 120 ℃ for 16 hours and drying, to obtain a poly (urea-urethane) material.
The material obtained in this comparative example does not contain polyaniline/graphene oxide, and as shown in fig. 3, the electrochemical impedance value is much lower than that of examples 1 to 3 when polyaniline/graphene oxide is not added.
As shown in fig. 4, it can be seen that the tensile strength of the self-healing anticorrosive material is improved to 3.35 times by using polyaniline/graphene oxide as a reinforcing material, but the elongation at break is not improved.
Comparative example 2
In comparative example 2, the polyaniline/graphene oxide composite material in example 1 was changed to polyaniline, and the other steps were the same as in example 1, and the specific operations were as follows:
2.3g of toluene-2, 4-diisocyanate-terminated polypropylene glycol are dissolved in 20 ml of N, N-dimethylformamide at 50 ℃ at ambient temperature; then, 0.16g of adipic acid dihydrazide was completely dissolved in 20 ml of hot N, N-dimethylformamide (120 ℃ C.), and the resultant solution was dropwise added to the above toluene-2, 4-diisocyanate-terminated polypropylene glycol solution with stirring, followed by magnetically stirring the mixed solution at a temperature of 120 ℃ for 16 hours; subsequently, 0.05g of polyaniline was dissolved in N, N-dimethylformamide, and after 1 hour of ultrasonic dispersion, the solution was added to the above mixed solution, and after stirring at normal temperature for 4 hours, the mixture was dried to obtain a poly (urea-urethane)/polyaniline composite material.
The material obtained in this comparative example was added with 2% polyaniline, and as shown in fig. 3, the electrochemical resistance value was significantly lower than that of examples 1 to 3, but significantly higher than that of comparative example 1.
Comparative example 3
In comparative example 3, the polyaniline/graphene oxide composite material in example 1 was changed to graphene oxide, and the other steps were the same as in example 1, and the specific operations were as follows:
2.3g of toluene-2, 4-diisocyanate-terminated polypropylene glycol are dissolved in 20 ml of N, N-dimethylformamide at 50 ℃ at ambient temperature; then, 0.16g of adipic acid dihydrazide was completely dissolved in 20 ml of hot N, N-dimethylformamide (120 ℃ C.), and the resultant solution was dropwise added to the above toluene-2, 4-diisocyanate-terminated polypropylene glycol solution with stirring, followed by magnetically stirring the mixed solution at a temperature of 120 ℃ for 16 hours; and then, dissolving 0.05g of graphene oxide in N, N-dimethylformamide, ultrasonically dispersing for 1 hour, adding the obtained solution into the mixed solution, stirring at normal temperature for 4 hours, and drying to obtain the poly (urea-urethane)/graphene oxide composite material.
The material obtained in this comparative example is added with 2% of graphene oxide, and as shown in fig. 3, the electrochemical resistance value is significantly lower than that of examples 1-3, but significantly higher than that of comparative example 1, and is also better than that of comparative example 2.
In the above examples and comparative examples, when the mass percentage of polyaniline/graphene oxide in the obtained poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material is 2%, the coating has better anticorrosive performance and has excellent tensile resistance and self-healing performance.
Claims (10)
1. A preparation method of a poly (urea-carbamate)/polyaniline/graphene oxide composite self-healing anticorrosive material is characterized by comprising the following steps:
(1) placing the hydrochloric acid solution of aniline in the graphene oxide turbid liquid, and stirring for 1-2 hours in an ice-water bath to obtain a stable mixed solution; continuously adding a hydrochloric acid solution of ammonium persulfate, stirring for 12-24 hours in an ice-water bath, standing, filtering, washing, and freeze-drying to obtain the polyaniline-graphene oxide composite material;
(2) and (2) dropwise adding an adipic acid dihydrazide N, N-dimethylformamide solution into an N, N-dimethylformamide solution of toluene-2, 4-diisocyanate terminated polypropylene glycol under stirring, reacting under stirring at 115-125 ℃ for 16-24 hours, adding the N, N-dimethylformamide dispersion liquid of the polyaniline-graphene oxide composite material obtained in the step (1), stirring at normal temperature for 4-8 hours, and drying to obtain the anticorrosive material.
2. The method of claim 1, wherein the aniline concentration in the hydrochloric acid solution of aniline is 0.2 moles/liter and the hydrogen chloride concentration is 0.2 moles/liter; the concentration of ammonium persulfate in the hydrochloric acid solution of ammonium persulfate was 0.13 mol/liter, and the concentration of hydrogen chloride was 0.2 mol/liter.
3. The method according to claim 1, wherein the mass ratio of aniline to graphene oxide is 10-20: 1; the molar ratio of hydrogen chloride to aniline in the hydrochloric acid solution of aniline is 0.5-1.5: 1; the molar ratio of ammonium persulfate to aniline is 0.5-2: 1.
4. The method according to claim 1, wherein the mass ratio of the graphene oxide to the water in the graphene oxide suspension is 0.0005 to 0.002: 1.
5. The method according to claim 1, wherein the mass concentration of the toluene-2, 4-diisocyanate terminated polypropylene glycol in the N, N-dimethylformamide solution of the toluene-2, 4-diisocyanate terminated polypropylene glycol is 9 to 15%, the mass concentration of the adipic acid dihydrazide in the N, N-dimethylformamide solution of the adipic acid dihydrazide is 0.6 to 1.1%, and the mass ratio of the toluene-2, 4-diisocyanate terminated polypropylene glycol to the adipic acid dihydrazide is 14.25 to 14.5: 1.
6. The method of claim 1, wherein the temperature of the N, N-dimethylformamide solution of toluene-2, 4-diisocyanate terminated polypropylene glycol is 45 to 60 ℃; the temperature of the N, N-dimethylformamide solution of adipic dihydrazide is 100-120 ℃.
7. The method of claim 1, wherein the mass ratio of the polyaniline-graphene oxide composite material to the toluene-2, 4-diisocyanate terminated polypropylene glycol is 1:46, and the mass ratio of the toluene-2, 4-diisocyanate terminated polypropylene glycol to the adipic acid dihydrazide is 57.5: 4.
8. The poly (urea-urethane)/polyaniline/graphene oxide composite self-healing anticorrosive material prepared by the method according to any one of claims 1 to 7.
9. The corrosion protection material of claim 8, comprising a polyaniline/graphene oxide composite and a poly (urea-urethane).
10. The anticorrosive material of claim 8, wherein the mass fraction of the polyaniline/graphene oxide composite material is 1% to 3% of the total mass of the anticorrosive material.
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| US20170051167A1 (en) * | 2013-07-04 | 2017-02-23 | Fondazione Istituto Italiano Di Tecnologia | Method for the preparation of polyaniline/reduced graphene oxide composites |
| CN107602805A (en) * | 2017-09-27 | 2018-01-19 | 江苏固格澜栅防护设施有限公司 | Room temperature Self-repair Composites and preparation method thereof |
| CN110698706A (en) * | 2019-11-22 | 2020-01-17 | 中国科学院深圳先进技术研究院 | Nano composite material and preparation method thereof |
| CN111205631A (en) * | 2020-02-28 | 2020-05-29 | 青岛科技大学 | Self-repairing polyurethane elastomer by electric heating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170051167A1 (en) * | 2013-07-04 | 2017-02-23 | Fondazione Istituto Italiano Di Tecnologia | Method for the preparation of polyaniline/reduced graphene oxide composites |
| CN107602805A (en) * | 2017-09-27 | 2018-01-19 | 江苏固格澜栅防护设施有限公司 | Room temperature Self-repair Composites and preparation method thereof |
| CN110698706A (en) * | 2019-11-22 | 2020-01-17 | 中国科学院深圳先进技术研究院 | Nano composite material and preparation method thereof |
| CN111205631A (en) * | 2020-02-28 | 2020-05-29 | 青岛科技大学 | Self-repairing polyurethane elastomer by electric heating and preparation method thereof |
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