CN111117320A - Fe2+/Fe3+Self-repairing agent for induced self-repairing nanotube and preparation method and application thereof - Google Patents
Fe2+/Fe3+Self-repairing agent for induced self-repairing nanotube and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
Abstract
The invention relates to Fe2+/Fe3+The nanotube self-repairing agent is obtained by electrostatic spinning of a tube core and a tube wall, the tube wall is pretreated polyvinyl alcohol, the tube core is cyclohexyl 3,4, 5-trihydroxybenzoic acid, and the mass ratio of the tube core to the tube wall is 1 (80-150), wherein the cyclohexyl 3,4, 5-trihydroxybenzoic acid is prepared by esterification reaction of gallic acid and cyclohexanol under the action of a catalyst. The repairing agent of the invention, the pipe wall of which is coated with the cyclohexyl 3,4, 5-trihydroxybenzoate, is arranged in the nano pipeThe fluidity or the directional mobility are not restricted, once microcracks occur at a certain position, the repairing agent can quickly reach the damaged part, the repairing agent and iron ions generate a chelation reaction to generate a stable chelate to realize self-repairing on the damaged part, the repairing agent has good self-repairing capability, and when the coating generates microcracks, the self-triggering can be self-triggered to repair the cracks, so that the service life of the coating is prolonged.
Description
Technical Field
The invention relates to Fe2+/Fe3+An induced self-repairing nano tube self-repairing agent, a preparation method and application thereof belong to the technical field of metal corrosion prevention.
Background
The latest corrosion investigation result shows that the total corrosion cost of China in 2014, including the loss and the corrosion prevention investment caused by corrosion, accounts for about 3.34 percent of GDP in the year, the total amount of the Chinese currency exceeds 21000 hundred million RMB, and the total corrosion cost is equivalent to 1555 yuan borne by each Chinese in the year. If appropriate corrosion protection measures can be taken, 30-40% of the economic losses due to corrosion can be recovered. In order to effectively relieve the corrosion phenomenon of steel structure facilities, the most direct and effective method is to adopt anticorrosive paint. In the using process of the anticorrosive paint, the surface of the coating is impacted and scratched, and some microscopic defects such as micropores, gaps, cracks and the like are generated in the curing process of the coating due to volatilization of an organic solvent and crosslinking or polycondensation of macromolecules, and the service life of the coating is seriously influenced by the existence of the defects, so that the coating fails.
Chinese patent document CN102796439A discloses a solvent-free nano-modified epoxy weather-resistant anticorrosive paint and a preparation method thereof. The coating is prepared by treating silicon-coated nano titanium dioxide particles with silane coupling agents KH-560 with epoxy groups, so that the surfaces of composite particles are provided with the epoxy groups, the epoxy groups participate in polymerization reaction, and the epoxy groups and epoxy resin have good interaction, so that the interaction force between the particles and the interface formed by polymers is enhanced, the interface has ideal bonding energy, the dispersibility of nanoparticles in the resin is improved, and the weather resistance of a composite coating is improved. The coating has no self-repairing function, and easily generates micro defects after a long time, so that the coating fails.
Therefore, for the repair of the microcracks, the coating with the self-repair function is produced at the same time, but the existing self-repair coating has complex trigger repair mechanism, is not easy to trigger repair and has long repair time.
Gallic acid (3, 4, 5-trihydroxybenzoic acid) is a kind of gallic acid, and when the carboxyl group of gallic acid reacts with alcohol to form esterified product, it can increase its lipid solubility. 3 phenolic hydroxyl groups in the molecules of the gallic acid ester are in ortho positions, are proton donors, show active reducibility and can generate chelation reaction with metal ions to generate stable compounds. When the iron-based metal is corroded, Fe is generated in the anode area2+/Fe3+If gallic acid compounds exist, Fe will be generated in the anode region2+/Fe3+A chelation reaction occurs to generate a stable chelate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Fe2+/Fe3+An induced self-repairing nanotube self-repairing agent, a preparation method and application thereof.
The invention can realize the following purposes:
1. the self-repairing function of the epoxy coating can be obviously endowed, self-service triggering can be realized, cracks can be repaired, the repairing agent is prevented from being fixed by the coating and being incapable of moving quickly or moving directionally, the coating is not bound, the repairing agent can reach the damaged part quickly, and directional and quick self-repairing is realized.
2. The self-repairing agent has low cost and is non-toxic and harmless.
In order to realize the purpose, the invention is realized by the following technical scheme:
fe2+/Fe3+The nanotube self-repairing agent is obtained by electrostatic spinning of a tube core and a tube wall, the tube wall is pretreated polyvinyl alcohol, the tube core is 3,4, 5-trihydroxybenzoic acid cyclohexyl ester, and the mass ratio of the tube core to the tube wall is 1 (80-150).
According to the invention, the cyclohexyl 3,4, 5-trihydroxybenzoate is prepared by esterification of gallic acid and cyclohexanol under the action of a catalyst.
According to the invention, the molar ratio of the gallic acid to the cyclohexanol is preferably 2-4: 30-50.
Most preferably, the molar ratio of the gallic acid to the cyclohexanol is 3: 20.
according to the invention, the catalyst is p-toluenesulfonic acid, and the molar ratio of the gallic acid to the catalyst is (10-15): (1-1.5).
Most preferably, the molar ratio of the gallic acid to the catalyst is 10: 1.
according to the preferable method, the esterification reaction comprises the steps of firstly stirring the mixture at 65-75 ℃ for 0.5-2 h, then stirring the mixture at 115 ℃ for reaction for 1.5-3 h, and naturally cooling the mixture to room temperature.
According to the invention, the pre-treated polyvinyl alcohol is preferably polyvinyl alcohol which is obtained by continuously stirring the polyvinyl alcohol at 85-95 ℃ for 24-48 h.
Fe2+/Fe3+The preparation method of the self-repairing agent for the induced self-repairing nanotube comprises the following steps:
taking cyclohexyl 3,4, 5-trihydroxy benzoate as a core layer spinning solution, pretreating polyvinyl alcohol as an outer layer spinning solution, and then carrying out coaxial electrostatic spinning to obtain Fe2+/Fe3+Inducing a self-repairing agent of the self-repairing nanotube.
According to the invention, the coaxial electrostatic spinning pressure is preferably 25-29V, and the spindle distance is preferably 15-25 cm.
Most preferably, the coaxial electrospinning pressure is 27.53V.
According to the invention, the advancing speed of the pipe wall material is 0.10-0.15mm/min and the advancing speed of the pipe core material is 0.001-0.003mm/min during coaxial electrostatic spinning.
Fe2+/Fe3+The application of the induced self-repairing nano tube self-repairing agent is used for preparing the epoxy self-repairing coating by adding the induced self-repairing nano tube self-repairing agent into the epoxy coating, wherein the addition amount of the self-repairing agent accounts for 10-20% of the epoxy coating.
Fe of the invention2+/Fe3+The self-repairing agent for the induced self-repairing nanotube ensures the directionality of the repairing agent for the nanometer tubular structure of the pretreated polyvinyl alcohol coated 3,4, 5-trihydroxybenzoic acid cyclohexyl ester, prevents the pretreatment polyvinyl alcohol from reacting with the cyclohexyl esterThe epoxy resin reacts to change the performance of the body coating, and the repairing agent is prevented from being fixed by the coating and being incapable of moving fast or moving directionally, the flowability or directional mobility of the repairing agent with the pipe wall coated with the 3,4, 5-trihydroxybenzoic acid cyclohexyl ester in the nano tube is not restricted, once microcrack occurs at a certain position, the repairing agent can quickly reach the damaged part, the repairing agent and iron ions generate chelation reaction, and stable chelate is generated to realize self-repairing on the damaged part, so that the effect of fast self-repairing is achieved.
The invention has the characteristics and advantages that:
(1) the self-repairing agent disclosed by the invention is simple in synthesis method, low in price, safe and low in cost. As described above, the reaction conditions of the present invention are mild and no additional harsh reaction conditions are required.
(2) The self-repairing agent can obviously endow the epoxy coating with a self-repairing function, improve the anti-corrosion capability and prolong the service life. As can be seen from the schematic diagram 2, the coating has good self-repairing capability, and can be triggered by self to repair cracks and prolong the service life of the coating when the coating is microcracked.
(3) The raw materials of the invention are ubiquitous in natural environment, nontoxic, low in price, high in safety and free of pollution to the environment.
Drawings
FIG. 1 is an SEM image of a self-healing agent prepared in example 1 of the present invention.
FIG. 2 is a graph showing the impedance spectrum of the damaged coating material in 3.5% NaCl solution for different periods of time in example 1 of the present invention.
FIG. 3 is a laser micrograph of a damaged coating after soaking in 3.5% NaCl solution for 0h according to example 1 of the present invention.
FIG. 4 is a laser micrograph of a damaged coating according to example 1 of the present invention after 6 days of repair with 3.5% NaCl solution.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
Example 1
Fe2+/Fe3+The preparation method of the self-repairing agent for the induced self-repairing nanotube comprises the following steps:
1) preparation of die material cyclohexyl 3,4, 5-trihydroxybenzoate: 0.06M gallic acid and 0.4M cyclohexanol were placed in a four-necked flat bottom flask, stirred at room temperature, followed by the addition of 0.006M p-toluene sulfonic acid. Stirring the mixture of the three for 1h at 70 ℃, then heating to 115 ℃ and keeping for 6h, and naturally cooling the obtained product to room temperature to obtain 3,4, 5-trihydroxy benzoic acid cyclohexyl ester;
2) the pipe wall material is pretreated with polyvinyl alcohol. Weighing 50g of polyvinyl alcohol, and continuously stirring at 90 ℃ for 24 hours to obtain pretreated polyvinyl alcohol;
3) preparing the nanotube: taking cyclohexyl 3,4, 5-trihydroxy benzoate as a core layer spinning solution, pretreating polyvinyl alcohol as an outer layer spinning solution, and then carrying out coaxial electrostatic spinning to obtain Fe2+/Fe3+Inducing a self-repairing agent for the self-repairing nanotube; the electrospinning pressure was 25.73V, the spindle distance was 20cm, the advancing speed of the tube wall material was 0.1mm/min, and the advancing speed of the tube core material was 0.001 mm/min.
The SEM image of the self-repairing agent prepared by the embodiment is shown in FIG. 1, and as can be seen from FIG. 1, the self-repairing agent has a nanotube-shaped structure of a tube wall and a tube core.
And (3) mixing a self-repairing agent with the epoxy coating, wherein the addition amount of the self-repairing agent accounts for 15% of the epoxy coating, and preparing the epoxy self-repairing coating.
Example 2
Fe2+/Fe3+The preparation method of the self-repairing agent for the induced self-repairing nanotube comprises the following steps:
1) preparation of die material cyclohexyl 3,4, 5-trihydroxybenzoate: 0.05M gallic acid and 0.75M cyclohexanol were placed in a four-necked flat bottom flask, stirred at room temperature, followed by the addition of 0.008M p-toluene sulfonic acid. Stirring the mixture of the three for 1.5h at 75 ℃, then heating to 110 ℃ for 6h, and naturally cooling the obtained product to room temperature to obtain the cyclohexyl 3,4, 5-trihydroxybenzoate;
2) the pipe wall material is pretreated with polyvinyl alcohol. Measuring 60g of polyvinyl alcohol, and continuously stirring at 85 ℃ for 24 hours to obtain pretreated polyvinyl alcohol;
3) preparing the nanotube: taking cyclohexyl 3,4, 5-trihydroxy benzoate as a core layer spinning solution, pretreating polyvinyl alcohol as an outer layer spinning solution, and then carrying out coaxial electrostatic spinning to obtain Fe2+/Fe3+Inducing a self-repairing agent for the self-repairing nanotube; the electrospinning pressure is 26.73, the spindle distance is 20cm, the advancing speed of the pipe wall material is 0.12mm/min, and the advancing speed of the pipe core material is 0.002 mm/min.
And (3) mixing a self-repairing agent with the epoxy coating, wherein the addition amount of the self-repairing agent accounts for 10% of the epoxy coating, and preparing the epoxy self-repairing coating.
Application test example
The epoxy self-repairing coating prepared in example 1 was selected, and the repair behavior of the coating (after artificial damage) in a 3.5% sodium chloride solution was studied by using an electrochemical impedance spectroscopy technique and using a three-electrode system (see fig. 2). The experimental results are shown in the schematic diagrams 2, 3 and 4. By analyzing the obtained electrochemical impedance spectrum, it can be seen that the coating has an initial impedance modulus value of 8.12X 103Ω·cm2After 6 days of soaking, the self-repairing impedance modulus of the coating is increased to 2.09 multiplied by 105Ω·cm2Has better repairing capability and the best repairing effect can be achieved in 6 days. And the resistance mode value of the coating began to decrease after 6 days of immersion.
Comparative test example
The repairing agent is cyclohexyl 3,4, 5-trihydroxybenzoate, the repairing agent is mixed with the epoxy coating, the addition amount of the self-repairing agent accounts for 15% of the epoxy coating, and the epoxy self-repairing coating is prepared.
After the epoxy self-repairing coating is artificially damaged, the repairing behavior in a 3.5% sodium chloride solution is observed, and a test result shows that the repairing agent cannot realize self-repairing in a quick and directional manner.
Claims (10)
1. Fe2+/Fe3+Self-repairing agent for inducing self-repairing nanotubeThe nanotube self-repairing agent is obtained by electrostatic spinning of a tube core and a tube wall, the tube wall is pretreated polyvinyl alcohol, the tube core is 3,4, 5-trihydroxybenzoic acid cyclohexyl ester, and the mass ratio of the tube core to the tube wall is 1 (80-150).
2. Fe of claim 12+/Fe3+The self-repairing agent for the induced self-repairing nanotube is characterized in that the cyclohexyl 3,4, 5-trihydroxybenzoate is prepared by esterification reaction of gallic acid and cyclohexanol under the action of a catalyst.
3. Fe according to claim 22+/Fe3+The induced self-repairing nano tube self-repairing agent is characterized in that the molar ratio of gallic acid to cyclohexanol is 2-4: 30-50; most preferably, the molar ratio of gallic acid to cyclohexanol is 3: 20.
4. fe according to claim 22+/Fe3+The self-repairing agent for the induced self-repairing nanotube is characterized in that the catalyst is p-toluenesulfonic acid, and the molar ratio of gallic acid to the catalyst is (10-15): (1-1.5); preferably, the molar ratio of gallic acid to catalyst is 10: 1.
5. fe according to claim 22+/Fe3+The self-repairing agent for the induced self-repairing nano tube is characterized in that the esterification reaction comprises the steps of firstly stirring the mixture at 65-75 ℃ for 0.5-2 h, then stirring the mixture at 115 ℃ for reaction for 1.5-3 h, and naturally cooling the mixture to room temperature.
6. Fe of claim 12+/Fe3+The self-repairing agent for the induced self-repairing nanotube is characterized in that the pretreated polyvinyl alcohol is obtained by continuously stirring polyvinyl alcohol at 85-95 ℃ for 24-48 hours.
7. Fe2+/Fe3+The preparation method of the self-repairing agent for the induced self-repairing nanotube comprises the following steps:
taking cyclohexyl 3,4, 5-trihydroxy benzoate as a core layer spinning solution, pretreating polyvinyl alcohol as an outer layer spinning solution, and then carrying out coaxial electrostatic spinning to obtain Fe2+/Fe3+Inducing a self-repairing agent of the self-repairing nanotube.
8. The method according to claim 7, wherein the coaxial electrospinning pressure is 25 to 29V, the spindle distance is 15 to 25cm, and preferably, the coaxial electrospinning pressure is 27.53V.
9. The method of claim 7, wherein the tube wall material is advanced at a speed of 0.10-0.15mm/min and the tube core material is advanced at a speed of 0.001-0.003mm/min during the coaxial electrospinning.
10. Fe2+/Fe3+The application of the induced self-repairing nano tube self-repairing agent is used for preparing the epoxy self-repairing coating by adding the induced self-repairing nano tube self-repairing agent into the epoxy coating, wherein the addition amount of the self-repairing agent accounts for 10-20% of the epoxy coating.
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