CN113683956A - Preparation method of graphene-silicon dioxide bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating - Google Patents

Preparation method of graphene-silicon dioxide bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating Download PDF

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CN113683956A
CN113683956A CN202110994890.2A CN202110994890A CN113683956A CN 113683956 A CN113683956 A CN 113683956A CN 202110994890 A CN202110994890 A CN 202110994890A CN 113683956 A CN113683956 A CN 113683956A
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graphene
silicon dioxide
polyaniline
graphene oxide
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高晓辉
李玉峰
张念飞
刘丽爽
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Qiqihar University
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Abstract

A preparation method of a graphene-silicon dioxide bonded grafted polyaniline/waterborne epoxy-containing silicon resin composite coating relates to a preparation method of an anticorrosive coating. The method aims to solve the problems that polyaniline and graphene are easy to aggregate and the preparation process is complex. The method comprises the following steps: anchoring silicon dioxide on the surface of graphene oxide through a covalent bond to prepare a graphene oxide-silicon dioxide composite material, preparing a graphene-silicon dioxide bonded grafted polyaniline composite material by using a silane coupling agent as a modifier, and preparing epoxy-containing aqueous silicone resin and compounding the epoxy-containing aqueous silicone resin with the graphene-silicon dioxide bonded grafted polyaniline composite material to obtain a composite coating. The invention improves the dispersibility of polyaniline and graphene, the synergistic effect of the silane coupling agent bonding grafting composite technology on the graphene and the polyaniline is more obvious, the corrosion resistance of the coating is effectively improved, the process is simple, and the environment-friendly effect is realized. The method is suitable for preparing the epoxy silicon resin composite anticorrosive coating.

Description

Preparation method of graphene-silicon dioxide bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating
Technical Field
The invention relates to a preparation method of an anticorrosive coating.
Background
Corrosion is an unavoidable natural process, particularly metals and alloys, which are extremely susceptible to chemical reactions with the environment and are gradually destroyed, with enormous annual energy and material losses. Therefore, the method has very important significance for the research on the prevention of corrosion. The method mainly has two means for avoiding metal corrosion, firstly, the corrosion-resistant material is developed by starting from the material, but the development cost and the preparation cost of the method are higher. Secondly, the existing materials are protected by a protection technology which mainly comprises electrochemical protection, coating protection, a corrosion inhibitor and the like, wherein the coating protection is most economical and effective and is widely researched and used by people.
Traditionally, polymers are commonly used in corrosion resistant coatings to create a barrier between the metal surface and the surrounding environment, preventing the penetration of corrosive ions through the coating to the metal surface, thereby protecting the metal from corrosion. The traditional coating material brings harm to human health and environment due to volatilization of organic solvent. Aqueous coatings using water as a solvent or dispersant are the current direction of development for corrosion protection coatings.
However, a pure polymer coating can only play a certain barrier role, the performance is not very ideal, and researches show that the corrosion resistance of the coating to metal can be effectively improved by adding a corrosion-resistant functional material into the polymer coating. The most common material used heretofore is chromate, which protects metals such as Q235 steel, AA7075, etc. from corrosion, but has limited use worldwide due to the toxicity and carcinogenicity of chromium ions. Therefore, a non-toxic and environment-friendly material is needed to replace chromate-containing materials to solve the corrosion problem.
The graphene is a two-dimensional nanosheet layer material, is environment-friendly when being used as a functional filler of a water-based coating, and has an ultra-large specific surface area, so that a good shielding effect can be achieved. Graphene sheets by overlappingCan form a compact impervious layer and prolong H2O、O2And Na+、Cl-The invasion path of plasma corrosion ions is improved, thereby improving the anti-corrosion performance of the composite coating. However, due to the high specific surface area and strong van der waals forces, graphene sheets tend to aggregate together, limiting their use in composite coating materials.
Polyaniline is one of the most potential conductive polymers as an anticorrosion filler instead of chromate. Polyaniline is a conductive polymer material with wide application, has good corrosion resistance to metals and alloys, and has the advantages of stability, environmental friendliness, easiness in synthesis and the like. However, polyaniline is insoluble and infusible due to its conjugated structure, has poor processability and poor dispersibility in aqueous resins, and thus has limited performance of its corrosion resistance.
Compounding of graphene and polyaniline is a direction of attention of researchers in recent years, and excellent performance of graphene and polyaniline can be comprehensively utilized. However, the improvement effect of the mixing and non-bonding compounding of graphene and polyaniline on the dispersibility of graphene and polyaniline, particularly in aqueous resin, is not ideal, and the exertion of the synergistic effect of graphene and polyaniline is limited. Moreover, a series of modifications are carried out on the graphene and the polyaniline, so that the preparation process is complex; or a large amount of organic solvents and chemicals are used, so that the production cost is high, and the wide application of the composite material is restricted.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a graphene-silicon dioxide bonded grafted polyaniline/waterborne epoxy-containing silicon resin composite coating.
The preparation method of the graphene-silicon dioxide bonded grafted polyaniline/waterborne epoxy-containing silicon resin composite coating comprises the following steps:
firstly, preparing a graphene oxide-silicon dioxide composite material
Adding graphene oxide into deionized water, performing ultrasonic dispersion for 3-4 hours to obtain a graphene oxide dispersion solution, then adding ammonia water, performing magnetic stirring for 15min to obtain an alkaline graphene oxide dispersion solution, then adding a mixed solution of absolute ethyl alcohol, deionized water and tetraethoxysilane, performing stirring reaction for 6 hours at 60 ℃, performing suction filtration and washing until a solid product becomes neutral, and obtaining a graphene oxide-silicon dioxide composite material;
the concentration of the graphene oxide dispersion liquid is 1-1.5 mg/mL;
the ratio of the volume of the ethyl orthosilicate to the mass of the graphene oxide in the first step is 50 mL: 1 mg;
the mass fraction of the ammonia water is 25 wt%, and the volume ratio of the ammonia water to the tetraethoxysilane is 1: 1;
the volume ratio of the absolute ethyl alcohol to the deionized water to the tetraethoxysilane is 80: 15: 5;
firstly, in-situ hydrolysis is carried out on ethyl orthosilicate on the surface of a graphene oxide sheet layer, and silicon dioxide is anchored on the surface of graphene oxide through a covalent bond to prepare the graphene oxide-silicon dioxide composite material.
Secondly, preparing the graphene-silicon dioxide bonded grafted polyaniline composite material
Adding the graphene oxide-silicon dioxide composite material obtained in the step one into 100mL of deionized water, stirring for 30min to form a dispersion liquid, adding a silane coupling agent, stirring at 60 ℃, performing reflux reaction for 6h, and cooling to room temperature; placing a reflux reaction device in an ice water bath at 3-5 ℃, adjusting the pH value of a reaction solution to 1 by using hydrochloric acid, adding aniline, magnetically stirring for 30min, finally dropwise adding an ammonium persulfate aqueous solution as an initiator, magnetically stirring for 6-8h, performing suction filtration after completion, washing a solid product to be neutral by using deionized water, and performing freeze drying on the solid product for 48h to obtain the graphene-silicon dioxide bonded grafted polyaniline composite material;
the mass ratio of the silane coupling agent to the graphene oxide in the first step is 20: 1;
the mass ratio of the aniline to the graphene oxide in the first step is 3: 1;
the mass ratio of ammonium persulfate to aniline in the ammonium persulfate aqueous solution is 3: 1;
and secondly, adopting a silane coupling agent as a modifier to carry out surface modification on the graphene oxide-silicon dioxide composite material to obtain silane modified silicon dioxide/graphene oxide, introducing an aniline monomer into a dispersion liquid of the silane modified silicon dioxide/graphene oxide, and synthesizing polyaniline on the surface of the graphene-silicon dioxide lamella by using a chemical bonding effect and an in-situ polymerization method to obtain the graphene-silicon dioxide bonded grafted polyaniline composite material with good dispersibility.
Thirdly, preparing the epoxy-containing waterborne silicone resin
Adding deionized water and absolute ethyl alcohol into a reagent bottle, then adding citric acid, performing ultrasonic treatment until the citric acid is completely dissolved, continuously adding tetraethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane into the reagent bottle, and stirring and reacting for 8 hours at the temperature of 40 ℃ to obtain the waterborne epoxy-containing silicon resin;
the mass ratio of the deionized water to the absolute ethyl alcohol is 2: 1;
the citric acid is 1-1.5% of the total mass of deionized water, absolute ethyl alcohol, ethyl orthosilicate, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane;
the mass ratio of the ethyl orthosilicate, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the dimethyl diethoxy silane is 5: 12: 4;
the ratio of the total mass of deionized water and absolute ethyl alcohol to the total mass of tetraethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane is 1: 1;
fourthly, preparing the water-based composite anti-corrosion coating
Grafting the graphene-silicon dioxide bonded polyaniline composite material (GO-SiO) obtained in the second step2-PANI) is evenly dispersed in the waterborne epoxy-containing silicon resin obtained in the third step by ultrasonic, then the mixture is coated on the surface of metal or alloy, and is heated and cured at 50 ℃ to obtain the graphene-silicon dioxide bonded and grafted polyaniline/waterborne epoxy-containing silicon resin composite coating (GO-SiO)2-PANI/ESiR)；
The addition amount of the graphene-silicon dioxide bonded grafted polyaniline composite material in the aqueous epoxy-containing silicon resin is 1.5-3.5 wt.%.
And step four, adding the graphene-silicon dioxide bonded grafted polyaniline composite material serving as a functional filler into the aqueous epoxy-containing silicon resin to be uniformly dispersed, and preparing the aqueous composite anticorrosive coating with excellent performance on the surface of the metal or alloy.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a graphene-silicon dioxide bonded grafted polyaniline composite material, which is prepared by anchoring silicon dioxide nano particles on the surface of graphene, modifying the graphene by using a silane coupling agent and bonding grafted polyaniline. Moreover, the invention also provides a film forming material taking the water-based epoxy-containing silicon resin as a composite coating.
Firstly, the anchoring of the silica nanoparticles increases the distance between graphene sheets and improves the dispersibility of graphene. According to the invention, the method of in-situ hydrolysis and hydroxyl condensation of ethyl orthosilicate on the surface of the graphene oxide sheet layer is adopted, and silicon dioxide is anchored on the surface of graphene oxide through a covalent bond.
Secondly, after the silane coupling agent is modified, amino groups, epoxy groups and other groups in the silane coupling agent molecules can be chemically bonded with aniline, so that polyaniline can uniformly cover the surfaces of silicon dioxide and graphene sheets, and the dispersibility of the polyaniline is also improved. Compared with a blending composite technology and a non-bonding composite technology of graphene and polyaniline, the silane coupling agent bonding grafting composite technology provided by the invention can effectively avoid the agglomeration of polyaniline and graphene in a composite coating, so that the dispersibility of the graphene-silicon dioxide bonding grafting polyaniline composite material in aqueous resin is improved.
Thirdly, the bonding graft compounding of the graphene, the silicon dioxide and the polyaniline enables the blocking effect of the graphene sheet layer and the passivation effect of the polyaniline to be better and synergistically exerted, and further the corrosion resistance of the composite coating is improved. Polyaniline is used as a nano wedge-shaped object to be uniformly bonded and grafted on the surface of graphene-silicon dioxide, so that the interlayer spacing of graphene sheets is further enlarged, and the dispersibility of graphene and the compatibility of the graphene sheets and a high polymer matrix are improved. Meanwhile, polyaniline fills the structural defects of graphene sheet layers, so that graphene sheetsLayer pair H2O、O2And Na+、Cl-The barrier range of the corrosive medium is more continuous, and the anti-permeability performance of the corrosive medium is improved. The graphene sheet layer enhances the barrier effect of the coating, enhances the conductivity and electrochemical activity of polyaniline, promotes the passivation effect of polyaniline and metal, and accelerates the generation of a passivation film, thereby further improving the corrosion resistance of the graphene-silicon dioxide bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating. Compared with the blending composite technology and the non-bonding composite technology of graphene and polyaniline, the silane coupling agent bonding grafting composite technology provided by the invention has more obvious synergistic effect on graphene and polyaniline.
Fourthly, an epoxy group is introduced into the organic silicon resin, and the organic silicon resin is solidified into a film through a three-dimensional network formed by the reaction of the organic silicon resin and the graphene-silicon dioxide bonded and grafted polyaniline composite material, so that the graphene-silicon dioxide bonded and grafted polyaniline/waterborne epoxy-containing silicon resin composite coating is more compact. The existing organic silicon resin coating has the advantages of low surface energy, good hydrophobicity, strong binding force with metal base materials and the like, and is widely applied to the field of anti-corrosion coating materials, but the existing organic silicon resin has higher curing temperature and is difficult to construct. According to the invention, the epoxy group is introduced into the organic silicon resin, so that the graphene-silicon dioxide bonded grafted polyaniline participates in the curing reaction of the epoxy-containing silicon resin, the curing condition of the silicon resin is improved, and the curing is completed at a relatively low temperature. Moreover, the graphene-silicon dioxide bonded grafted polyaniline is uniformly introduced into the silicone resin coating as a curing agent, so that the corrosion resistance of the coating is effectively improved.
Fifthly, the graphene-silicon dioxide bonded grafted polyaniline composite material provided by the invention has good dispersibility in water-based resin, improves the corrosion resistance of the composite coating, realizes the water-based performance of the anti-corrosion coating, and is environment-friendly.
Sixth, the graphene-silicon dioxide bonded and grafted polyaniline composite anticorrosive coating provided by the invention has excellent anticorrosive capacity, and can be widely applied to the metal fields of steel, aluminum alloy, magnesium alloy and the likeAnd the environment such as acid, alkali, salt and the like, and has long-term corrosion protection effect on metals under harsher conditions such as marine environment and the like. The corrosion current density of the Q235 steel coated with the coating of the invention is only 1.28 multiplied by 10-9A/cm2The corrosion rate is only 9.90 multiplied by 10-6mm/year. The barrier property and the durability are excellent, and the impedance value of the composite coating can reach 3.13 multiplied by 10 at most8Ω·cm2After soaking in 3.5 wt% NaCl water solution for 504h, the impedance value is still maintained at 1.26 × 108Ω·cm2。
The invention is compared with the prior art which is closer:
compared with CN112048228A, namely a silica-polyaniline-graphene modified epoxy resin anticorrosive material:
1. the silicon dioxide-polyaniline-graphene modified epoxy resin anticorrosive material disclosed by the document comprises the following process routes: (1) reacting monochloroacetic acid with graphene oxide to obtain carboxylated graphene, and reacting with p-phenylenediamine to obtain aminated graphene; (2) reacting silicon dioxide with vinyl trimethoxy silane to obtain vinyl silicon dioxide, and adding potassium permanganate and concentrated sulfuric acid to obtain carboxylated silicon dioxide; (3) adding 5-sulfosalicylic acid into concentrated sulfuric acid to obtain a mixed acid solution, and adding polyvinylpyrrolidone, aniline, aminated graphene and carboxylated silicon dioxide to obtain a mixed solution. Taking a quarter volume of mixed acid solution, adding ammonium persulfate to obtain an ammonium persulfate mixed acid solution, dropwise adding the ammonium persulfate mixed acid solution into the mixed solution, carrying out in-situ polymerization on the aminated graphene and aniline under the initiation of the ammonium persulfate, replacing H in COOH with polyaniline, and grafting through a valence bond to form the silicon dioxide-polyaniline-graphene composite material; (4) adding n-butyl alcohol and the silicon dioxide-polyaniline-graphene composite material into xylene to obtain a mixed solution, adding the xylene, the n-butyl alcohol and the epoxy resin into another reaction bottle, uniformly stirring, pouring into the mixed solution, and adding a T-31 curing agent to obtain the silicon dioxide-polyaniline-graphene modified epoxy resin anticorrosive material.
2. Compared with the document, the graphene-silicon dioxide bonded grafted polyaniline/waterborne epoxy-containing silicon resin composite coating adopts different processes: (1) according to the method, the silicon dioxide is anchored on the surface of the graphene oxide through a covalent bond by adopting a method of in-situ hydrolysis and hydroxyl condensation of ethyl orthosilicate on the surface of the graphene oxide sheet layer. The silicon dioxide is prepared by in-situ hydrolysis and condensation on the surface of a graphene sheet layer, and is not compounded with graphene modified in series after the existing silicon dioxide is modified in series; (2) the polyaniline is grafted on the surface of graphene-silicon dioxide through silane coupling agent bonding, and after the silane coupling agent is modified, amino groups, epoxy groups and other groups in aniline molecules and silane coupling agent molecules really realize covalent bonding, so that H in COOH is replaced; (3) the silicon dioxide anchoring on the surface of the graphene oxide and the further bonding and grafting of polyaniline are a series of continuous processes, and the aminated graphene, the carboxylated silicon dioxide and the like are not separately mixed; (4) the invention provides a film forming material taking water-based epoxy-containing silicon resin as a composite coating, which does not use an organic solvent.
3. Compared with the literature, the beneficial effects of the different processes of the invention are as follows: (1) the silicon dioxide nano particles are anchored on the surface of the graphene sheet layer through in-situ hydrolysis and hydroxyl condensation of ethyl orthosilicate on the surface of the graphene sheet layer, so that the distance between the graphene sheet layers is increased, and the effect of improving the dispersibility of graphene is more remarkable. (2) Amino groups, epoxy groups and other groups in the silane coupling agent molecules can be combined with aniline through covalent bonds, so that polyaniline can uniformly cover the surfaces of silicon dioxide and graphene sheets, and the dispersibility of the polyaniline is also improved. Thereby improving the dispersibility of the graphene-silicon dioxide bonded grafted polyaniline composite material in the aqueous resin. (3) The silane coupling agent bonding grafting composite technology has more obvious synergistic effect on graphene and polyaniline. The polyaniline fills the structural defects of the graphene sheet layer, and improves the anti-permeability performance to corrosive media. The graphene enhances the electrochemical activity of polyaniline and promotes the passivation effect of polyaniline and metal, so that the corrosion resistance of the graphene-silicon dioxide bonded and grafted polyaniline/waterborne epoxy-containing silicon resin composite coating is further improved. Q235 steel corrosion current coated with coating of the inventionDensity of only 1.28X 10-9A/cm2Lower than the test results of this document; (4) according to the invention, a series of processes of anchoring silicon dioxide on the surface of graphene oxide and further bonding and grafting polyaniline are continuously completed, and the process is simple. Chemical medicines such as monochloroacetic acid, p-phenylenediamine, potassium permanganate, concentrated sulfuric acid, 5-sulfosalicylic acid, polyvinylpyrrolidone and the like are not used in the preparation process, so that the cost is relatively low; (5) the preparation method has the advantages that the water-based epoxy-containing silicon resin which is low in surface energy, good in hydrophobicity and strong in binding force with a metal substrate is used as a film forming material of the composite coating, on one hand, the graphene-silicon dioxide bonded grafted polyaniline is uniformly introduced into the silicon resin coating in the form of a curing agent and participates in the curing reaction of the epoxy-containing silicon resin, so that the curing condition of the silicon resin is improved, the compactness of the composite coating is increased, and the corrosion resistance of the coating is effectively improved. On the other hand, organic solvents such as dimethylbenzene and n-butyl alcohol are not used, emission of organic volatile compounds (VOC) is reduced, and environmental friendliness is achieved.
4. Compared with the document, the invention (1) further solves the problem of agglomeration of graphene and polyaniline, and improves the dispersibility of the graphene-silicon dioxide bonded and grafted polyaniline composite material in aqueous resin by anchoring silicon dioxide nano particles on the surface of graphene and bonding and grafting polyaniline with a silane coupling agent; (2) the problem that the synergistic effect of graphene and polyaniline is not ideal is further solved, the polyaniline is grafted by anchoring of silicon dioxide nano particles on the surface of graphene and bonding of a silane coupling agent, so that the barrier effect of a graphene sheet layer and the passivation effect of the polyaniline are better and synergistically exerted, and the corrosion resistance of the composite coating is further improved; (3) the problems of complex preparation process and high cost of the graphene/polyaniline composite anticorrosive coating are solved, and a series of continuous methods of in-situ condensation and bonding grafting are adopted, so that the process is simple and the cost is relatively low; (4) the problem of environmental pollution of organic solvents and chemicals is solved, the water-based epoxy-containing silicon resin is used as a film forming material of the composite coating, the compactness of the composite coating is good, the emission of organic volatile matters is reduced, and the environment friendliness is realized.
Secondly, compared with CN111675901A, a silicon dioxide-graphene oxide modified polyaniline anticorrosive material and a preparation method thereof, the invention has the following advantages:
1. the process route of the silicon dioxide-graphene oxide modified polyaniline anticorrosive material disclosed by the document is as follows: (1) in a nitrogen atmosphere, adding graphene oxide into a toluene solvent, and taking azobisisobutyronitrile as an initiator to prepare cyano-modified graphene oxide; (2) adding sodium hydroxide and cyano-modified graphene oxide into an ethanol solvent, and hydrolyzing the cyano-modified graphene oxide under an alkaline condition to prepare carboxylated graphene with high carboxyl content; (3) adding thionyl chloride and carboxylated graphene into a flask, carrying out reflux reaction in a nitrogen atmosphere, adding toluene, carrying out reduced pressure distillation, removing redundant thionyl chloride, and preparing and obtaining acylchlorinated graphene; (4) adding acylchlorinated graphene into an anhydrous tetrahydrofuran solvent, adding 4- (BOC-amino) phenol, carrying out reflux reaction in a nitrogen atmosphere, adding excessive trifluoroacetic acid and dichloromethane, removing BOC protective groups, and washing and drying with methanol to obtain aminated graphene; (5) adding nano silicon dioxide, isocyanatopropyl triethoxysilane and chitosan into an absolute ethanol solvent, adding glacial acetic acid until the chitosan is dissolved, condensing, refluxing, washing and drying to prepare silicon dioxide-chitosan; (6) adding perfluoroheptanoic acid, ammonium persulfate, aniline, silica-chitosan and aminated graphene into a 2% acetic acid solution, filtering, washing and drying a product by using an acetone solution, and preparing the silica-graphene oxide modified polyaniline.
2. Compared with the document, the graphene-silicon dioxide bonded grafted polyaniline/waterborne epoxy-containing silicon resin composite coating adopts different processes: (1) according to the method, the silicon dioxide is anchored on the surface of the graphene oxide through a covalent bond by adopting a method of in-situ hydrolysis and hydroxyl condensation of ethyl orthosilicate on the surface of the graphene oxide sheet layer. The silicon dioxide is prepared by in-situ hydrolysis and condensation on the surface of a graphene sheet layer, and is not compounded with a series of modified graphene after the existing nano silicon dioxide and chitosan are compounded; (2) the polyaniline is grafted on the surface of graphene-silicon dioxide through silane coupling agent bonding, amino groups, epoxy groups and other groups in aniline molecules and silane coupling agent molecules really realize covalent bonding after the silane coupling agent is modified, and free amino groups contained in a chitosan molecular structure are used for grafting polyaniline, so that the processability of the polyaniline is improved; (3) the silicon dioxide anchoring on the surface of graphene oxide and the further bonding grafting of polyaniline are a series of continuous processes, and the literature refers to a series of modifications from cyano-modified graphene oxide, carboxylated graphene and acylchlorinated graphene to aminated graphene, which are separately carried out with silicon dioxide-chitosan and then compounded with aniline and the like; (4) the invention provides a film forming material taking water-based epoxy-containing silicon resin as a composite coating.
3. Compared with the literature, the beneficial effects of the different processes of the invention are as follows: (1) the silicon dioxide nano particles are anchored on the surface of the graphene sheet layer through in-situ hydrolysis and hydroxyl condensation of ethyl orthosilicate on the surface of the graphene sheet layer, so that the distance between the graphene sheet layers is increased, and the effect of improving the dispersibility of graphene is more remarkable. (2) Amino groups, epoxy groups and other groups in the silane coupling agent molecules can be combined with aniline through covalent bonds, so that polyaniline can uniformly cover the surfaces of silicon dioxide and graphene sheets, and the dispersibility of the polyaniline is also improved. Thereby improving the dispersibility of the graphene-silicon dioxide bonded grafted polyaniline composite material in the aqueous resin. (3) The silane coupling agent bonding grafting composite technology has more obvious synergistic effect on graphene and polyaniline. The polyaniline fills the structural defects of the graphene sheet layer, and improves the anti-permeability performance to corrosive media. The electrochemical activity of polyaniline is enhanced by the graphene, and the passivation effect of polyaniline and metal is promoted, so that the corrosion resistance of the graphene-silicon dioxide bonded and grafted polyaniline/waterborne epoxy-containing silicon resin composite coating is further improved; (4) according to the invention, a series of continuous completion of anchoring silicon dioxide on the surface of graphene oxide and further bonding and grafting polyaniline is carried out, a series of modifications from cyano-modified graphene oxide, carboxylated graphene, acylchlorinated graphene to aminated graphene and the like are not required, and the process is simple. Chemical medicines such as nitrogen, toluene, sodium hydroxide, thionyl chloride, tetrahydrofuran, 4- (BOC-amino) phenol, trifluoroacetic acid, dichloromethane, methanol, isocyanatopropyl triethoxysilane, glacial acetic acid, perfluoroheptanoic acid, acetone and the like are not used in the preparation process, so that the cost is relatively low; (5) the preparation method has the advantages that the water-based epoxy-containing silicon resin which is low in surface energy, good in hydrophobicity and strong in binding force with a metal substrate is used as a film forming material of the composite coating, on one hand, the graphene-silicon dioxide bonded grafted polyaniline is uniformly introduced into the silicon resin coating in the form of a curing agent and participates in the curing reaction of the epoxy-containing silicon resin, so that the curing condition of the silicon resin is improved, the compactness of the composite coating is increased, and the corrosion resistance of the coating is effectively improved. On the other hand, organic solvents such as dimethylbenzene and n-butyl alcohol are not used, emission of organic volatile compounds (VOC) is reduced, and environmental friendliness is achieved.
4. Compared with the document, the invention (1) further solves the problem of agglomeration of graphene and polyaniline, and improves the dispersibility of the graphene-silicon dioxide bonded and grafted polyaniline composite material in aqueous resin by anchoring silicon dioxide nano particles on the surface of graphene and bonding and grafting polyaniline with a silane coupling agent; (2) the problem that the synergistic effect of graphene and polyaniline is not ideal is further solved, the polyaniline is grafted by anchoring of silicon dioxide nano particles on the surface of graphene and bonding of a silane coupling agent, so that the barrier effect of a graphene sheet layer and the passivation effect of the polyaniline are better and synergistically exerted, and the corrosion resistance of the composite coating is further improved; (3) the problems of complex preparation process and high cost of the graphene/polyaniline composite anticorrosive coating are solved, and a series of continuous methods of in-situ condensation and bonding grafting are adopted, so that the process is simple and the cost is relatively low; (4) the problem of environmental pollution of organic solvents and chemicals is solved, the water-based epoxy-containing silicon resin is used as a film forming material of the composite coating, the compactness of the composite coating is good, the emission of organic volatile matters is reduced, and the environment friendliness is realized.
Drawings
Fig. 1 is a scanning electron micrograph of the graphene-silica bonded grafted polyaniline composite material prepared in step two of example 1;
FIG. 2 is a TEM image of the graphene-silica bonded grafted polyaniline composite prepared in step two of example 1;
FIG. 3 is the electrochemical impedance spectrum of different coatings in 3.5% NaCl solution;
FIG. 4 is a graph of electrochemical impedance spectra of different coatings after soaking in 3.5% NaCl solution for 504 hours;
FIG. 5 is a plot of polarization curves for different composite coatings;
fig. 6 is a schematic diagram of an anticorrosion mechanism of the graphene-silica/silicone resin composite coating (a) and the graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicone resin composite coating (b).
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and any reasonable combination of the specific embodiments is included.
The first embodiment is as follows: the preparation method of the graphene-silicon dioxide bonded grafted polyaniline/waterborne epoxy-containing silicon resin composite coating comprises the following steps:
firstly, preparing a graphene oxide-silicon dioxide composite material
Adding graphene oxide into deionized water, performing ultrasonic dispersion for 3-4 hours to obtain a graphene oxide dispersion solution, then adding ammonia water, performing magnetic stirring for 15min to obtain an alkaline graphene oxide dispersion solution, then adding a mixed solution of absolute ethyl alcohol, deionized water and tetraethoxysilane, performing stirring reaction for 6 hours at 60 ℃, performing suction filtration and washing until a solid product becomes neutral, and obtaining a graphene oxide-silicon dioxide composite material;
the concentration of the graphene oxide dispersion liquid is 1-1.5 mg/mL;
the ratio of the volume of the ethyl orthosilicate to the mass of the graphene oxide in the first step is 50 mL: 1 mg;
the mass fraction of the ammonia water is 25 wt%, and the volume ratio of the ammonia water to the tetraethoxysilane is 1: 1;
the volume ratio of the absolute ethyl alcohol to the deionized water to the tetraethoxysilane is 80: 15: 5;
firstly, in-situ hydrolysis is carried out on ethyl orthosilicate on the surface of a graphene oxide sheet layer, and silicon dioxide is anchored on the surface of graphene oxide through a covalent bond to prepare the graphene oxide-silicon dioxide composite material.
Secondly, preparing the graphene-silicon dioxide bonded grafted polyaniline composite material
Adding the graphene oxide-silicon dioxide composite material obtained in the step one into 100mL of deionized water, stirring for 30min to form a dispersion liquid, adding a silane coupling agent, stirring at 60 ℃, performing reflux reaction for 6h, and cooling to room temperature; placing a reflux reaction device in an ice water bath at 3-5 ℃, adjusting the pH value of a reaction solution to 1 by using hydrochloric acid, adding aniline, magnetically stirring for 30min, finally dropwise adding an ammonium persulfate aqueous solution as an initiator, magnetically stirring for 6-8h, performing suction filtration after completion, washing a solid product to be neutral by using deionized water, and performing freeze drying on the solid product for 48h to obtain the graphene-silicon dioxide bonded grafted polyaniline composite material;
the mass ratio of the silane coupling agent to the graphene oxide in the first step is 20: 1;
the mass ratio of the aniline to the graphene oxide in the first step is 3: 1;
the mass ratio of ammonium persulfate to aniline in the ammonium persulfate aqueous solution is 3: 1;
and secondly, adopting a silane coupling agent as a modifier to carry out surface modification on the graphene oxide-silicon dioxide composite material to obtain silane modified silicon dioxide/graphene oxide, introducing an aniline monomer into a dispersion liquid of the silane modified silicon dioxide/graphene oxide, and synthesizing polyaniline on the surface of the graphene-silicon dioxide lamella by using a chemical bonding effect and an in-situ polymerization method to obtain the graphene-silicon dioxide bonded grafted polyaniline composite material with good dispersibility.
Thirdly, preparing the epoxy-containing waterborne silicone resin
Adding deionized water and absolute ethyl alcohol into a reagent bottle, then adding citric acid, performing ultrasonic treatment until the citric acid is completely dissolved, continuously adding tetraethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane into the reagent bottle, and stirring and reacting for 8 hours at the temperature of 40 ℃ to obtain the waterborne epoxy-containing silicon resin;
the mass ratio of the deionized water to the absolute ethyl alcohol is 2: 1;
the citric acid is 1-1.5% of the total mass of deionized water, absolute ethyl alcohol, ethyl orthosilicate, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane;
the mass ratio of the ethyl orthosilicate, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the dimethyl diethoxy silane is 5: 12: 4;
the ratio of the total mass of deionized water and absolute ethyl alcohol to the total mass of tetraethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane is 1: 1;
fourthly, preparing the water-based composite anti-corrosion coating
Grafting the graphene-silicon dioxide bonded polyaniline composite material (GO-SiO) obtained in the second step2-PANI) is evenly dispersed in the waterborne epoxy-containing silicon resin obtained in the third step by ultrasonic, then the mixture is coated on the surface of metal or alloy, and is heated and cured at 50 ℃ to obtain the graphene-silicon dioxide bonded and grafted polyaniline/waterborne epoxy-containing silicon resin composite coating (GO-SiO)2-PANI/ESiR)；
The addition amount of the graphene-silicon dioxide bonded grafted polyaniline composite material in the aqueous epoxy-containing silicon resin is 1.5-3.5 wt.%.
And step four, adding the graphene-silicon dioxide bonded grafted polyaniline composite material serving as a functional filler into the aqueous epoxy-containing silicon resin to be uniformly dispersed, and preparing the aqueous composite anticorrosive coating with excellent performance on the surface of the metal or alloy.
The embodiment has the following beneficial effects:
the graphene-silica bonded grafted polyaniline composite material provided by the embodiment is prepared by anchoring silica nanoparticles on the surface of graphene, modifying the graphene with a silane coupling agent, and bonding grafted polyaniline. Moreover, the embodiment also provides the film forming material of the water-based epoxy-containing silicon resin as the composite coating.
Firstly, the anchoring of the silica nanoparticles increases the distance between graphene sheets and improves the dispersibility of graphene. According to the embodiment, the method that ethyl orthosilicate is subjected to in-situ hydrolysis and hydroxyl condensation on the surface of a graphene oxide sheet layer is adopted, and silicon dioxide is anchored on the surface of graphene oxide through a covalent bond.
Secondly, after the silane coupling agent is modified, amino groups, epoxy groups and other groups in the silane coupling agent molecules can be chemically bonded with aniline, so that polyaniline can uniformly cover the surfaces of silicon dioxide and graphene sheets, and the dispersibility of the polyaniline is also improved. Compared with a blending composite technology and a non-bonding composite technology of graphene and polyaniline, the silane coupling agent bonding grafting composite technology provided by the embodiment can effectively avoid the agglomeration of polyaniline and graphene in a composite coating, so that the dispersibility of the graphene-silicon dioxide bonding grafting polyaniline composite material in aqueous resin is improved.
Thirdly, the bonding graft compounding of the graphene, the silicon dioxide and the polyaniline enables the blocking effect of the graphene sheet layer and the passivation effect of the polyaniline to be better and synergistically exerted, and further the corrosion resistance of the composite coating is improved. Polyaniline is used as a nano wedge-shaped object to be uniformly bonded and grafted on the surface of graphene-silicon dioxide, so that the interlayer spacing of graphene sheets is further enlarged, and the dispersibility of graphene and the compatibility of the graphene sheets and a high polymer matrix are improved. Meanwhile, polyaniline fills the structural defects of graphene sheet layers, so that the graphene sheet layers are opposite to H2O、O2And Na+、Cl-The barrier range of the corrosive medium is more continuous, and the anti-permeability performance of the corrosive medium is improved. The graphene sheet layer enhances the barrier effect of the coating, enhances the conductivity and electrochemical activity of polyaniline, promotes the passivation effect of polyaniline and metal, and accelerates the generation of a passivation film, thereby further improving the corrosion resistance of the graphene-silicon dioxide bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating. Compared with a blending composite technology and a non-bonding composite technology of graphene and polyaniline, the silane coupling agent bonding grafting composite technology provided by the embodiment has a more obvious synergistic effect on graphene and polyaniline.
Fourthly, an epoxy group is introduced into the organic silicon resin, and the organic silicon resin is solidified into a film through a three-dimensional network formed by the reaction of the organic silicon resin and the graphene-silicon dioxide bonded and grafted polyaniline composite material, so that the graphene-silicon dioxide bonded and grafted polyaniline/waterborne epoxy-containing silicon resin composite coating is more compact. The existing organic silicon resin coating has the advantages of low surface energy, good hydrophobicity, strong binding force with metal base materials and the like, and is widely applied to the field of anti-corrosion coating materials, but the existing organic silicon resin has higher curing temperature and is difficult to construct. According to the embodiment, the epoxy group is introduced into the organic silicon resin, so that the graphene-silicon dioxide bonded grafted polyaniline participates in the curing reaction of the epoxy-containing silicon resin, the curing condition of the silicon resin is improved, and the curing is completed at a relatively low temperature. Moreover, the graphene-silicon dioxide bonded grafted polyaniline is uniformly introduced into the silicone resin coating as a curing agent, so that the corrosion resistance of the coating is effectively improved.
Fifth, the graphene-silica bonded grafted polyaniline composite material provided by the embodiment has good dispersibility in aqueous resin, realizes the water-based anticorrosion coating while improving the anticorrosion performance of the composite coating, and is environment-friendly.
Sixth, the graphene-silica bonded and grafted polyaniline composite anticorrosive coating provided by the embodiment has excellent anticorrosive ability, can be widely applied to the metal fields such as steel, aluminum alloy, magnesium alloy and the like, and the environments such as acid, alkali, salt and the like, and has a long-term corrosion protection effect on metals under severe conditions such as marine environment and the like. The corrosion current density of the Q235 steel coated with the coating of the embodiment is only 1.28 multiplied by 10-9A/cm2The corrosion rate is only 9.90 multiplied by 10-6mm/year. The barrier property and the durability are excellent, and the impedance value of the composite coating can reach 3.13 multiplied by 10 at most8Ω·cm2After soaking in 3.5 wt% NaCl water solution for 504h, the impedance value is still maintained at 1.26 × 108Ω·cm2。
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: adding graphene oxide into deionized water, performing ultrasonic dispersion for 3.5 hours to obtain a graphene oxide dispersion solution, then adding ammonia water, performing magnetic stirring for 15 minutes to obtain an alkaline graphene oxide dispersion solution, then adding a mixed solution of absolute ethyl alcohol, deionized water and tetraethoxysilane, performing stirring reaction for 6 hours at 60 ℃, performing suction filtration and washing until a solid product becomes neutral, and thus obtaining the graphene oxide-silicon dioxide composite material.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: step two, adding the graphene oxide-silicon dioxide composite material obtained in the step one into 100mL of deionized water, stirring for 30min to form a dispersion liquid, adding a silane coupling agent, stirring at 60 ℃, performing reflux reaction for 6h, and cooling to room temperature; placing a reflux reaction device in an ice-water bath at 4 ℃, adjusting the pH value of a reaction solution to 1 by using hydrochloric acid, adding aniline, magnetically stirring for 30min, finally dropwise adding an ammonium persulfate aqueous solution as an initiator, magnetically stirring for 7h, performing suction filtration after completion, washing a solid product with deionized water to be neutral, and performing freeze drying on the solid product for 48h to obtain the graphene-silicon dioxide bonded grafted polyaniline composite material.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: in the first step, the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH560) or N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane (KH 792).
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the third step, the citric acid is 1.2 percent of the total mass of the deionized water, the absolute ethyl alcohol, the ethyl orthosilicate, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the dimethyl diethoxy silane.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: in the third step, the metal is steel.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the alloy in the third step is aluminum alloy, magnesium alloy and the like.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: in the fourth step, the addition amount of the graphene-silicon dioxide bonded grafted polyaniline composite material in the aqueous epoxy-containing silicon resin is 3 wt.%.
Example 1:
the preparation method of the graphene-silicon dioxide bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating comprises the following steps:
firstly, preparing a graphene oxide-silicon dioxide composite material
Adding graphene oxide into deionized water, performing ultrasonic dispersion for 3-4 hours to obtain a graphene oxide dispersion solution, then adding ammonia water, performing magnetic stirring for 15min to obtain an alkaline graphene oxide dispersion solution, then adding a mixed solution of absolute ethyl alcohol, deionized water and tetraethoxysilane, performing stirring reaction for 6 hours at 60 ℃, performing suction filtration and washing until a solid product becomes neutral, and obtaining a graphene oxide-silicon dioxide composite material;
the concentration of the graphene oxide dispersion liquid is 1-1.5 mg/mL;
the ratio of the volume of the ethyl orthosilicate to the mass of the graphene oxide in the first step is 50 mL: 1 mg;
the mass fraction of the ammonia water is 25 wt%, and the volume ratio of the ammonia water to the tetraethoxysilane is 1: 1;
the volume ratio of the absolute ethyl alcohol to the deionized water to the tetraethoxysilane is 80: 15: 5;
firstly, in-situ hydrolysis is carried out on ethyl orthosilicate on the surface of a graphene oxide sheet layer, and silicon dioxide is anchored on the surface of graphene oxide through a covalent bond to prepare the graphene oxide-silicon dioxide composite material.
Secondly, preparing the graphene-silicon dioxide bonded grafted polyaniline composite material
Adding the graphene oxide-silicon dioxide composite material obtained in the step one into 100mL of deionized water, stirring for 30min to form a dispersion liquid, adding a silane coupling agent, stirring at 60 ℃, performing reflux reaction for 6h, and cooling to room temperature; placing a reflux reaction device in an ice-water bath at 4 ℃, adjusting the pH value of a reaction solution to 1 by using hydrochloric acid, adding aniline, magnetically stirring for 30min, finally dropwise adding an ammonium persulfate aqueous solution as an initiator, magnetically stirring for 7h, performing suction filtration after completion, washing a solid product with deionized water to be neutral, and performing freeze drying on the solid product for 48h to obtain the graphene-silicon dioxide bonded grafted polyaniline composite material;
the mass ratio of the silane coupling agent to the graphene oxide in the first step is 20: 1, the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (KH 560);
the mass ratio of the aniline to the graphene oxide in the first step is 3: 1;
the mass ratio of ammonium persulfate to aniline in the ammonium persulfate aqueous solution is 3: 1;
and secondly, adopting a silane coupling agent as a modifier to carry out surface modification on the graphene oxide-silicon dioxide composite material to obtain silane modified silicon dioxide/graphene oxide, introducing an aniline monomer into a dispersion liquid of the silane modified silicon dioxide/graphene oxide, and synthesizing polyaniline on the surface of the graphene-silicon dioxide lamella by using a chemical bonding effect and an in-situ polymerization method to obtain the graphene-silicon dioxide bonded grafted polyaniline composite material with good dispersibility.
Thirdly, preparing the epoxy-containing waterborne silicone resin
Adding deionized water and absolute ethyl alcohol into a reagent bottle, then adding citric acid, performing ultrasonic treatment until the citric acid is completely dissolved, continuously adding tetraethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane into the reagent bottle, and stirring and reacting for 8 hours at the temperature of 40 ℃ to obtain the waterborne epoxy-containing silicon resin;
the mass ratio of the deionized water to the absolute ethyl alcohol is 2: 1;
the citric acid is 1.2 percent of the total mass of the deionized water, the absolute ethyl alcohol, the ethyl orthosilicate, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the dimethyl diethoxy silane;
the mass ratio of the ethyl orthosilicate, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the dimethyl diethoxy silane is 5: 12: 4;
the ratio of the total mass of deionized water and absolute ethyl alcohol to the total mass of tetraethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane is 1: 1;
fourthly, preparing the water-based composite anti-corrosion coating
The graphene-silicon dioxide obtained in the second stepBonded graft polyaniline composite material (GO-SiO)2-PANI) is evenly dispersed in the waterborne epoxy-containing silicon resin obtained in the third step by ultrasonic, then the mixture is coated on the surface of Mg-Li alloy, and is heated and cured at 50 ℃ to obtain the graphene-silicon dioxide bonded and grafted polyaniline/waterborne epoxy-containing silicon resin composite coating (GO-SiO)2-PANI/ESiR)；
The addition amount of the graphene-silicon dioxide bonded grafted polyaniline composite material in the aqueous epoxy-containing silicon resin is 3 wt.%;
and step four, adding the graphene-silicon dioxide bonded grafted polyaniline composite material serving as a functional filler into the aqueous epoxy-containing silicon resin to be uniformly dispersed, and preparing the aqueous composite anticorrosive coating with excellent performance on the surface of the metal or alloy.
Fig. 1 is a scanning electron micrograph of the graphene-silica bonded grafted polyaniline composite material prepared in step two of example 1; as can be seen from fig. 1, the circular and elliptical particles are uniformly distributed on the surface of the graphene sheet layer, which shows that the silicon dioxide is uniformly grafted to the surface of the graphene sheet layer, and the aniline is polymerized in situ on the silicon dioxide and the graphene sheet layer, so that the silicon dioxide particles and the graphene sheet layer are uniformly wrapped, thereby effectively avoiding the agglomeration of polyaniline and graphene in the composite coating, and improving the dispersibility of the graphene-silicon dioxide bonded grafted polyaniline in the aqueous resin.
FIG. 2 is a TEM image of the graphene-silica bonded grafted polyaniline composite prepared in step two of example 1; as can be seen from fig. 2, graphene having a lamellar structure and silica nanoparticles uniformly distributed on the surface of the lamellar layer are uniformly coated with polyaniline, and the successful preparation of the graphene-silica bonded grafted polyaniline composite material is further proved, and the dispersibility of the graphene lamellar layer and the silica bonded grafted polyaniline is good.
Comparative analysis step three, namely the prepared waterborne epoxy-containing silicon resin coating (ESiR), the graphene/waterborne epoxy-containing silicon resin composite coating (GO/ESiR) and the graphene-silicon dioxide/waterborne epoxy-containing silicon resin composite coating (GO-SiO)2ESiR) and graphene dioxy prepared in example 1Silicon-bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating (GO-SiO)2-PANI/ESiR); wherein GO and GO-SiO2、GO-SiO2The added amount of the PANI in the ESiR is 3 percent (mass fraction).
The preparation process of the graphene/water-based epoxy-containing silicon resin composite coating (GO/ESiR) comprises the following steps: ultrasonically dispersing Graphene Oxide (GO) in the waterborne epoxy-containing silicon resin obtained in the third step uniformly, coating the Graphene Oxide (GO) on the surface of Mg-Li alloy, and heating and curing at 50 ℃ to obtain a graphene/waterborne epoxy-containing silicon resin composite coating (GO/ESiR);
graphene-silica/silicone composite coating (GO-SiO)2ESiR) preparation process: preparing the graphene-silicon dioxide composite material (GO-SiO) obtained in the step one2) Uniformly dispersing the aqueous epoxy-containing silicon resin obtained in the step three in an ultrasonic manner, coating the aqueous epoxy-containing silicon resin on the surface of Mg-Li alloy, and heating and curing at 50 ℃ to obtain a graphene-silicon dioxide/aqueous epoxy-containing silicon resin composite coating (GO-SiO)2/ESiR)；
FIG. 3 is the electrochemical impedance spectrum of different coatings in 3.5% NaCl solution; as can be seen from the electrochemical impedance spectrogram, of the four coatings, graphene-silicon dioxide bonded and grafted polyaniline/aqueous epoxy-containing silicon resin composite coating (GO-SiO)2-PANI/ESiR) to reach 3.13 × 108Ω·cm2The method proves that the blocking effect of the graphene and the passivation effect of the polyaniline are better and synergistically exerted by the graphene-silicon dioxide bonded grafted polyaniline, and the corrosion resistance of the composite coating is obviously improved.
FIG. 4 is a graph of electrochemical impedance spectra of different coatings after soaking in 3.5% NaCl solution for 504 hours; the arc radius of the capacitive reactance gradually decreases along with the prolonging of the soaking time, which indicates that the corrosive medium gradually permeates into the metal surface through the coating. However, after soaking for 504 hours, graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating (GO-SiO)2the-PANI/ESiR) impedance value can still reach 1.26 multiplied by 108Ω·cm2Of the four coatings, graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating (GO-SiO)2PANI/ESiR) has better durability, and its good barrier and electrochemical protection properties can provide long-term corrosion protection to metals.
FIG. 5 is a plot of polarization curves for different composite coatings; as can be seen from the polarization curves, of the four coatings, graphene-silicon dioxide bonded grafted polyaniline/waterborne epoxy-containing silicon resin composite coating (GO-SiO)2-PANI/ESiR) has the lowest corrosion current density of 1.28X 10-9A/cm2The corrosion rate is only 9.90 multiplied by 10-6mm/year, the best corrosion resistance is shown.
Fig. 6 is a schematic diagram of an anticorrosion mechanism of the graphene-silica/silicone resin composite coating (a) and the graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicone resin composite coating (b). In fig. 6 (a): the silicon dioxide improves the dispersibility of the graphene in the water-based silicon resin, the uniformly dispersed graphene-silicon dioxide prolongs the diffusion path of a corrosive medium, and the anti-corrosion performance of the composite coating is improved. In fig. 6 (b): polyaniline is grafted on the surface of the graphene-silicon dioxide through chemical bonding of a silane coupling agent, so that the polyaniline is uniformly coated on the surface of the graphene-silicon dioxide, the dispersibility of the polyaniline in water-based silicone resin is improved, and the synergistic effect of the graphene and the polyaniline is enhanced. The polyaniline increases the blocking capability of the graphene sheet layer, the graphene enhances the electrochemical activity of the polyaniline, promotes the passivation effect of the polyaniline and metal, and accelerates the generation of a passivation film, thereby further improving the corrosion resistance.

Claims (8)

1. A preparation method of a graphene-silicon dioxide bonded grafted polyaniline/waterborne epoxy-containing silicon resin composite coating is characterized by comprising the following steps: the method comprises the following steps:
firstly, preparing a graphene oxide-silicon dioxide composite material
Adding graphene oxide into deionized water, performing ultrasonic dispersion for 3-4 hours to obtain a graphene oxide dispersion solution, then adding ammonia water, performing magnetic stirring for 15min to obtain an alkaline graphene oxide dispersion solution, then adding a mixed solution of absolute ethyl alcohol, deionized water and tetraethoxysilane, performing stirring reaction for 6 hours at 60 ℃, performing suction filtration and washing until a solid product becomes neutral, and obtaining a graphene oxide-silicon dioxide composite material;
the concentration of the graphene oxide dispersion liquid is 1-1.5 mg/mL;
the ratio of the volume of the ethyl orthosilicate to the mass of the graphene oxide in the first step is 50 mL: 1 mg;
the mass fraction of the ammonia water is 25 wt%, and the volume ratio of the ammonia water to the tetraethoxysilane is 1: 1;
the volume ratio of the absolute ethyl alcohol to the deionized water to the tetraethoxysilane is 80: 15: 5;
secondly, preparing the graphene-silicon dioxide bonded grafted polyaniline composite material
Adding the graphene oxide-silicon dioxide composite material obtained in the step one into 100mL of deionized water, stirring for 30min to form a dispersion liquid, adding a silane coupling agent, stirring at 60 ℃, performing reflux reaction for 6h, and cooling to room temperature; placing a reflux reaction device in an ice water bath at 3-5 ℃, adjusting the pH value of a reaction solution to 1 by using hydrochloric acid, adding aniline, magnetically stirring for 30min, finally dropwise adding an ammonium persulfate aqueous solution as an initiator, magnetically stirring for 6-8h, performing suction filtration after completion, washing a solid product to be neutral by using deionized water, and performing freeze drying on the solid product for 48h to obtain the graphene-silicon dioxide bonded grafted polyaniline composite material;
the mass ratio of the silane coupling agent to the graphene oxide in the first step is 20: 1;
the mass ratio of the aniline to the graphene oxide in the first step is 3: 1;
the mass ratio of ammonium persulfate to aniline in the ammonium persulfate aqueous solution is 3: 1;
thirdly, preparing the epoxy-containing waterborne silicone resin
Adding deionized water and absolute ethyl alcohol into a reagent bottle, then adding citric acid, performing ultrasonic treatment until the citric acid is completely dissolved, continuously adding tetraethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane into the reagent bottle, and stirring and reacting for 8 hours at the temperature of 40 ℃ to obtain the waterborne epoxy-containing silicon resin;
the mass ratio of the deionized water to the absolute ethyl alcohol is 2: 1;
the citric acid is 1-1.5% of the total mass of deionized water, absolute ethyl alcohol, ethyl orthosilicate, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane;
the mass ratio of the ethyl orthosilicate, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the dimethyl diethoxy silane is 5: 12: 4;
the ratio of the total mass of deionized water and absolute ethyl alcohol to the total mass of tetraethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and dimethyl diethoxy silane is 1: 1;
fourthly, preparing the water-based composite anti-corrosion coating
Grafting the graphene-silicon dioxide bonded polyaniline composite material (GO-SiO) obtained in the second step2-PANI) is evenly dispersed in the waterborne epoxy-containing silicon resin obtained in the third step by ultrasonic, then the mixture is coated on the surface of metal or alloy, and is heated and cured at 50 ℃ to obtain the graphene-silicon dioxide bonded and grafted polyaniline/waterborne epoxy-containing silicon resin composite coating (GO-SiO)2-PANI/ESiR)；
The addition amount of the graphene-silicon dioxide bonded grafted polyaniline composite material in the aqueous epoxy-containing silicon resin is 1.5-3.5 wt.%.
2. The preparation method of the graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating according to claim 1, which is characterized in that: adding graphene oxide into deionized water, performing ultrasonic dispersion for 3.5 hours to obtain a graphene oxide dispersion solution, then adding ammonia water, performing magnetic stirring for 15 minutes to obtain an alkaline graphene oxide dispersion solution, then adding a mixed solution of absolute ethyl alcohol, deionized water and tetraethoxysilane, performing stirring reaction for 6 hours at 60 ℃, performing suction filtration and washing until a solid product becomes neutral, and thus obtaining the graphene oxide-silicon dioxide composite material.
3. The preparation method of the graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating according to claim 1, which is characterized in that: step two, adding the graphene oxide-silicon dioxide composite material obtained in the step one into 100mL of deionized water, stirring for 30min to form a dispersion liquid, adding a silane coupling agent, stirring at 60 ℃, performing reflux reaction for 6h, and cooling to room temperature; placing a reflux reaction device in an ice-water bath at 4 ℃, adjusting the pH value of a reaction solution to 1 by using hydrochloric acid, adding aniline, magnetically stirring for 30min, finally dropwise adding an ammonium persulfate aqueous solution as an initiator, magnetically stirring for 7h, performing suction filtration after completion, washing a solid product with deionized water to be neutral, and performing freeze drying on the solid product for 48h to obtain the graphene-silicon dioxide bonded grafted polyaniline composite material.
4. The preparation method of the graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating according to claim 1, which is characterized in that: in the first step, the silane coupling agent is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane or N- (beta-aminoethyl) -gamma-aminopropyl trimethoxy silane.
5. The preparation method of the graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating according to claim 1, which is characterized in that: in the third step, the citric acid is 1.2 percent of the total mass of the deionized water, the absolute ethyl alcohol, the ethyl orthosilicate, the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and the dimethyl diethoxy silane.
6. The preparation method of the graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating according to claim 1, which is characterized in that: in the third step, the metal is steel.
7. The preparation method of the graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating according to claim 1, which is characterized in that: the alloy in the third step is aluminum alloy or magnesium alloy.
8. The preparation method of the graphene-silica bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating according to claim 1, which is characterized in that: in the fourth step, the addition amount of the graphene-silicon dioxide bonded grafted polyaniline composite material in the aqueous epoxy-containing silicon resin is 3 wt.%.
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