CN113604151B - Preparation method of phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating - Google Patents

Preparation method of phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating Download PDF

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CN113604151B
CN113604151B CN202110996062.2A CN202110996062A CN113604151B CN 113604151 B CN113604151 B CN 113604151B CN 202110996062 A CN202110996062 A CN 202110996062A CN 113604151 B CN113604151 B CN 113604151B
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polyaniline
graphene
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graphene oxide
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李玉峰
高晓辉
赵甜甜
赵阳
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Qiqihar University
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Abstract

A preparation method of a phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating relates to a preparation method of a silicon resin composite anticorrosive coating. The preparation method aims to solve the problems of poor dispersibility of modified graphene and polyaniline in high polymer resin, complex process and environmental pollution in the preparation of the conventional composite coating. The method comprises the following steps: silicon dioxide is anchored on the surface of graphene oxide through a covalent bond to prepare a graphene oxide-silicon dioxide composite material, phytic acid is used as a modifier to prepare a phosphated polyaniline-silicon dioxide graft modified graphene composite material, and the phosphated polyaniline-silicon dioxide graft modified graphene composite material is compounded and cured with epoxy group-containing waterborne silicone resin. The invention improves the dispersibility of graphene and polyaniline, improves the hydrophobicity of the composite coating, exerts the synergistic effect of graphene and polyaniline more obviously and improves the corrosion resistance of the water-based coating. The invention is suitable for preparing the preparation method of the silicon resin composite anticorrosive coating.

Description

Preparation method of phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating
Technical Field
The invention relates to a preparation method of a silicone resin composite anticorrosive coating.
Background
The metal material is an indispensable part for the life and social development of people, and the function of the metal material cannot be replaced. However, corrosion phenomena of metals are also very common. The annual economic losses due to metal corrosion are immeasurable. Therefore, the protection of metal is particularly important, and the effective protection of metal is always the aim pursued by people. Currently, there are many methods for metal protection. Among them, the most direct and effective method is to coat the surface of the substrate with an anticorrosive coating material, which can greatly prolong the service life of the metal.
Traditionally, polymers have been used in corrosion protection coatings to create a barrier between the metal surface and the surrounding environment, preventing corrosion ions from penetrating through the coating to the metal surface, thereby protecting the metal from corrosion. The coating can be classified into natural resins, acrylics, epoxies, polyurethanes, silicone resins, and the like according to the film-forming material. Among them, the organic silicon resin has good stability, oxidation resistance and corrosion resistance, and is one of the film forming materials with excellent performance at present. The oxysilanes may be hydrolyzed in aqueous solution by a "sol-gel" process, and the silane compounds may spontaneously form covalent bonds on the surface of the metal or alloy after hydrolysis. Such metal-oxygen-silicon bonds may form silicone resins by condensation reactions. The silicon atoms in the silicon resin can increase the number of alkoxy and covalent bonds formed on the surface of the metal or alloy, so that the electrolyte penetration resistance is enhanced, and the corrosion resistance of the coating is improved. However, when a film is formed, a large amount of solvent is volatilized, and cracks and micropores are formed to different degrees, so that the compactness of the coating is influenced, and the overall corrosion resistance of the coating is reduced. Moreover, conventional coating materials pose health and environmental hazards to humans due to volatilization of organic solvents. Aqueous coatings using water as a solvent or dispersant are the current direction of development for corrosion protection coatings.
The 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 addition of functional anti-corrosive fillers is an effective means to further improve the anti-corrosive properties of the coating, and is usually carried outContaining lamellar fillers for improving shielding properties and fillers having a metal corrosion inhibiting effect, e.g. clay or montmorillonite, TiO2Or Al2O3Rare earth, graphene, polyaniline, and the like.
Graphene is a carbon atom sp2The novel two-dimensional carbon nanomaterial which is only single atom layer thick and formed by the hybrid orbit has an ultra-large specific surface area, and excellent electrical conductivity, thermal conductivity, oxidation resistance and permeability resistance. The graphene can improve the shielding performance of the composite coating, and effectively block water, oxygen and other small molecules and Na+、Cl-The penetration of plasma corrosive ions has great application potential in the field of metal protective coatings. Although graphene has excellent properties, graphene is not an ideal hexagonal honeycomb lattice and two-dimensional structure in practice, and has many defects in structure, and oxidized groups of graphene oxide structurally form nano-pores. Graphene itself is not impenetrable. Moreover, 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. The defects of the graphene are improved, so that the graphene can be better dispersed, and the graphene can exert better performance. Dispersion of pure graphene or graphene oxide is difficult. The dispersion is generally carried out directly by physical means such as stirring or sonication. The unmodified simple mechanical dispersing effect is not ideal, and related researches are few. In order to improve the dispersion efficiency, a certain group modification is generally performed on the surface of graphene. The combination mode of the modifying group and the graphene is divided into covalent bonding and non-covalent bonding physical adsorption. Physical adsorption mechanisms include electrostatic adsorption, orbital conjugation, and hydrogen bonding. In the aspect of a dispersing agent or a modifying group, there are small organic molecules, organic polymers and inorganic nano-oxides. These improve the dispersibility of the modified graphene in the polymer resin.
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.
Due to the excellent lamellar barrier effect of the graphene, the graphene can be used as a filler to improve the corrosion resistance of the coating; polyaniline is widely used in anticorrosive coatings due to its excellent electrical conductivity and redox properties. After the two fillers are effectively compounded, the coating can show more excellent corrosion resistance. However, the improvement effect of the mixed and non-bonded composite 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; a large amount of organic solvents and chemical medicines are used, 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 phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating.
The preparation method of the phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating comprises the following steps:
firstly, preparing 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 volume ratio of the ethyl orthosilicate to the graphene oxide is 50 mL: 1 mg;
the mass fraction of the ammonia water is 25wt%, 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 phosphated polyaniline-silicon dioxide graft modified graphene 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, adding phytic acid, stirring at 100 ℃, performing reflux reaction for 10-12 h, and cooling to room temperature; placing the reflux reaction device in an ice water bath at 3-5 ℃, adjusting the pH value of a reaction solution to 1 by using phytic 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 a phosphated polyaniline-silicon dioxide grafted modified graphene composite material;
the ratio of the volume of the phytic acid to the mass of the graphene oxide in the first step is 50 mL: 1 mg;
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, carrying out surface modification on the graphene oxide-silicon dioxide composite material by adopting phytic acid as a modifier to obtain phytic acid modified silicon dioxide/graphene oxide, introducing an aniline monomer into a dispersion liquid of the phytic acid modified silicon dioxide/graphene oxide, and synthesizing polyaniline on the surface of the graphene-silicon dioxide lamella by utilizing a chemical bonding effect and an in-situ polymerization method to obtain the phosphorized polyaniline-silicon dioxide graft modified graphene 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
Ultrasonically dispersing the phosphated polyaniline-silicon dioxide graft modified graphene composite material obtained in the second step in the waterborne epoxy-containing silicon resin obtained in the third step uniformly, coating the mixture on the surface of metal or alloy, and heating and curing the mixture at 50 ℃ to obtain a phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating;
the addition amount of the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the water-based silicone resin is 1.5-3.5 wt.%.
And step four, adding the phosphated polyaniline-silicon dioxide graft modified graphene 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:
according to the invention, after the silicon dioxide nano particles are anchored on the surface of graphene, the graphene is modified by phytic acid, and then the grafted polyaniline is bonded, so that the phosphated polyaniline-silicon dioxide grafted modified graphene composite material is obtained.
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. Meanwhile, the silicon dioxide particles also increase the micro roughness of the surface of the graphene sheet layer, and are beneficial to improving the hydrophobicity of the composite coating.
And secondly, after the phytic acid is modified, phosphate groups in phytic acid 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 improved. Compared with the blending composite technology and the non-bonding composite technology of the graphene and the polyaniline, the phytic acid bonding and grafting composite technology provided by the invention can further effectively avoid the agglomeration of the polyaniline and the graphene in the composite coating, so that the dispersibility of the phosphated polyaniline-silicon dioxide grafting modified graphene composite material in the 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 phosphated polyaniline-silicon dioxide graft modified graphene/aqueous epoxy-containing silicon resinCorrosion resistance of the composite coating. Compared with the blending composite technology and the non-bonding composite technology of the graphene and the polyaniline, the phytic acid bonding grafting composite technology provided by the invention has more obvious synergistic effect on the graphene and the polyaniline.
Fourthly, in a patent simultaneously filed by the applicant and named as 'graphene-silicon dioxide bonded grafted polyaniline/waterborne epoxy-containing silicon resin composite coating', a silane coupling agent is adopted as a modifier to carry out surface modification on a graphene oxide-silicon dioxide composite material to obtain silane modified silicon dioxide/graphene oxide. The phytic acid is used for replacing a silane coupling agent, has the advantage that the phytic acid molecule contains six phosphate groups, and plays multiple roles in the process of modifying the surface of graphene-silicon dioxide, bonding and grafting polyaniline and protecting metal from corrosion. Firstly, phytic acid plays a role of a grafting modifier, while part of phosphate groups in phytic acid molecules act on the surface of graphene-silicon dioxide, the other part of phosphate groups are chemically bonded with aniline, so that polyaniline is uniformly covered on the surfaces of silicon dioxide and graphene sheets, and the dispersibility of graphene and polyaniline is further improved; and the phytic acid plays a role of a dopant, and the phytic acid is used as the dopant of the polyaniline, so that the conductivity and the electrochemical activity of the polyaniline can be improved. After the surface of the graphene-silicon dioxide is modified, a large-volume lamellar structure is introduced into the dopant counter ions, so that the barrier property of the polyaniline composite material is improved; thirdly, a plurality of phosphate groups of the phytic acid have a chelating effect with metals, a passivation film can be generated on the metal surface, the passivation effect of polyaniline on the metals is enhanced, and the corrosion resistance of the water-based coating is further improved.
Fifthly, an epoxy group is introduced into the organic silicon resin, and the organic silicon resin is cured to form a film through a three-dimensional network formed by the reaction of the organic silicon resin and the polyaniline-silicon dioxide graft modified graphene composite material, so that the polyaniline-silicon dioxide graft modified graphene/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. However, 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 phosphated polyaniline-silicon dioxide graft modified graphene 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. And the phosphated polyaniline-silicon dioxide grafted modified graphene is uniformly introduced into the silicone resin coating as a curing agent, so that the corrosion resistance of the coating is effectively improved.
Sixth, the phosphated polyaniline-silicon dioxide graft modified graphene 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 property of the anticorrosive coating, and is environment-friendly.
Seventh, the phosphated polyaniline-silica graft modified graphene composite anticorrosive coating provided by the invention has excellent anticorrosive capability, can be widely applied to the metal fields of steel, aluminum alloy, magnesium alloy and the like, and the environments of 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 Mg-Li alloy coated with the coating of the invention is only 8.55 multiplied by 10-9A/cm2The corrosion rate is only 8.82 multiplied by 10-4mm/year. The barrier property and the durability are excellent, and the impedance value of the composite coating can reach 4.06 multiplied by 10 at most9Ω·cm2The impedance value is maintained at 1.51 multiplied by 10 after soaking in 3.5 wt% NaCl solution for 360 hours6Ω·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 literature, the phosphated polyaniline-silicon dioxide graft modified graphene/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 phytic acid bonding, and after phytic acid is modified, aniline molecules are grafted on the surface of graphene-silicon dioxide through chemical bonding with phosphate ester groups in the phytic acid molecules; (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) The phosphate group in the phytic acid molecule can be chemically bonded with aniline, so that polyaniline can be uniformly covered on the surfaces of silicon dioxide and graphene sheets, and the dispersibility of the polyaniline is also improved. Thereby improving the dispersibility of the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the water-based resin. (3) The phytic acid bonding grafting composite technology has more obvious synergistic effect on the graphene and the 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 phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating is further improved; (4) the phytic acid molecule contains six phosphate groups, and plays multiple roles in the process of modifying the surface of graphene-silicon dioxide, bonding and grafting polyaniline and protecting metal from corrosion. The phytic acid is a grafting modifier between graphene-silicon dioxide and polyaniline, a doping agent of the polyaniline, and a metal chelating passivator. The phytic acid further improves the dispersibility of the graphene and the polyaniline, improves the conductivity, the electrochemical activity and the barrier property of the polyaniline, and enhances the passivation effect of the polyaniline on metals, thereby further improving the corrosion resistance of the aqueous coating. (5) 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; (6) 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 phosphated polyaniline-silicon dioxide graft modified graphene 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 literature, the invention (1) further solves the problem of agglomeration of graphene and polyaniline, and improves the dispersibility of the phosphated polyaniline-silica graft modified graphene composite material in aqueous resin by anchoring the silica nanoparticles on the surface of the graphene and bonding and grafting the polyaniline with phytic acid; (2) the problem that the synergistic effect of graphene and polyaniline is not ideal is further solved, the polyaniline is grafted by anchoring of the silicon dioxide nano particles on the surface of the graphene and bonding of phytic acid, so that the barrier effect of the 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 literature, the phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite anticorrosive 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 phytic acid bonding, after phytic acid is modified, aniline molecules and phosphate groups in the phytic acid molecules really realize chemical bonding, and free amino contained in a chitosan molecular structure is used for grafting with the 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) The phosphate group in the phytic acid molecule 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 improved. Thereby improving the dispersibility of the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the water-based resin. (3) The phytic acid bonding grafting composite technology has more obvious synergistic effect on the graphene and the 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 phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating is further improved; (4) the phytic acid molecule contains six phosphate groups, and plays multiple roles in the process of modifying the surface of graphene-silicon dioxide, bonding and grafting polyaniline and protecting metal from corrosion. The phytic acid is a grafting modifier between graphene-silicon dioxide and polyaniline, a doping agent of the polyaniline, and a metal chelating passivator. The phytic acid further improves the dispersibility of the graphene and the polyaniline, improves the conductivity, the electrochemical activity and the barrier property of the polyaniline, and enhances the passivation effect of the polyaniline on metals, thereby further improving the corrosion resistance of the aqueous coating. (5) 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 the cost is relatively low; (6) 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 phosphated polyaniline-silicon dioxide graft modified graphene 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 literature, the invention (1) further solves the problem of agglomeration of graphene and polyaniline, and improves the dispersibility of the phosphated polyaniline-silica graft modified graphene composite material in aqueous resin by anchoring the silica nanoparticles on the surface of the graphene and bonding and grafting the polyaniline with phytic acid; (2) the problem that the synergistic effect of graphene and polyaniline is not ideal is further solved, the polyaniline is grafted by anchoring of the silicon dioxide nano particles on the surface of the graphene and bonding of phytic acid, so that the barrier effect of the 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.
Thirdly, compared with CN 110054969A, an anticorrosive coating based on phytic acid modified graphene and a preparation method thereof, the invention has the advantages that:
1. the process route of the anticorrosive coating based on the phytic acid modified graphene in the document is as follows: adding graphene oxide and phytic acid into water, uniformly dispersing, and reacting at 80-100 ℃ to obtain phytic acid modified graphene; adding the phytic acid modified graphene into resin and uniformly dispersing to obtain the metal anticorrosive paint based on the phytic acid modified graphene.
2. Compared with the literature, the phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite anticorrosive coating adopts and adds different processes: (1) firstly, anchoring silicon dioxide on the surface of graphene oxide by covalent bonds by adopting a method of in-situ hydrolysis and hydroxyl condensation of ethyl orthosilicate on the surface of a graphene oxide sheet layer; (2) secondly, modifying the surface of the graphene-silicon dioxide by phytic acid bonding grafting; (3) after the phytic acid is modified, introducing an aniline monomer and an initiator, and bonding and grafting polyaniline on the surface of the graphene-silicon dioxide by using chemical bonding of amino groups in aniline molecules and phosphate ester groups in phytic acid molecules to prepare a phosphated polyaniline-silicon dioxide graft modified graphene composite material; (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) The phosphate group in the phytic acid molecule can be chemically bonded with aniline, so that polyaniline can be uniformly covered on the surfaces of silicon dioxide and graphene sheets, and the dispersibility of the polyaniline is also improved. Thereby improving the dispersibility of the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the water-based resin. (3) Polyaniline is bonded and grafted on the surface of the graphene-silicon dioxide by a phytic acid bonding and grafting composite technology, so that the polyaniline and the graphene can play a role in a synergistic manner. 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 phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating is further improved; (4) 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 prepared to be used as a film forming material of the composite coating, the phosphated polyaniline-silicon dioxide graft modified graphene 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, 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.
4. Compared with the literature, the invention (1) further solves the problem of agglomeration of graphene and polyaniline, and improves the dispersibility of the phosphated polyaniline-silica graft modified graphene composite material in aqueous resin by anchoring the silica nanoparticles on the surface of the graphene and bonding and grafting the polyaniline with phytic acid; (2) the problem that the synergistic effect of graphene and polyaniline is not ideal is further solved, the polyaniline is grafted by anchoring of the silicon dioxide nano particles on the surface of the graphene and bonding of phytic acid, so that the barrier effect of the 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.
Compared with CN110684462A, a phytate doped polyaniline/polyphenylene sulfone coating composition and a preparation method thereof:
1. the phytic acid doped polyaniline/polyphenylene sulfone coating composition disclosed by the document has the following process route: stirring the prepared aniline/N-methyl pyrrolidone/phytic acid solution at the water bath temperature of 20-40 ℃, dropwise adding the prepared ammonium persulfate/phytic acid solution, carrying out a full reaction for 4-6 hours to form a phytic acid doped polyaniline solid precipitate, carrying out reduced pressure filtration, fully washing the precipitate with ethanol with the mass fraction of 95% and deionized water respectively, and carrying out vacuum drying for 16-24 hours at the temperature of 20-40 ℃ to obtain the phytic acid doped polyaniline. Adding film-forming resin polyphenylene sulfone into a diluent at a stirring speed of 2000 r/min-2700 r/min, sequentially adding phytic acid doped polyaniline and other optional pigments, fillers and auxiliaries, raising the rotation speed to 3800 r/min-4500 r/min, and grinding for 4-8 hours to obtain the phytic acid doped polyaniline/polyphenylene sulfone coating composition.
2. Compared with the literature, the phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite anticorrosive coating adopts and adds different processes: (1) firstly, anchoring silicon dioxide on the surface of graphene oxide by covalent bonds by adopting a method of in-situ hydrolysis and hydroxyl condensation of ethyl orthosilicate on the surface of a graphene oxide sheet layer; (2) secondly, modifying the surface of the graphene-silicon dioxide by phytic acid bonding grafting; (3) after the phytic acid is modified, introducing an aniline monomer and an initiator, and bonding and grafting polyaniline on the surface of the graphene-silicon dioxide by using chemical bonding of amino groups in aniline molecules and phosphate ester groups in phytic acid molecules to prepare a phosphated polyaniline-silicon dioxide graft modified graphene composite material; (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) The phosphate group in the phytic acid molecule can be chemically bonded with aniline, so that polyaniline can be uniformly covered on the surfaces of silicon dioxide and graphene sheets, and the dispersibility of the polyaniline is also improved. Thereby improving the dispersibility of the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the water-based resin. (3) Polyaniline is bonded and grafted on the surface of the graphene-silicon dioxide by a phytic acid bonding and grafting composite technology, so that the polyaniline and the graphene can play a role in a synergistic manner. 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 phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating is further improved; (4) 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 prepared to be used as a film forming material of the composite coating, the phosphated polyaniline-silicon dioxide graft modified graphene 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, 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. Moreover, polyphenylene sulfone is not used, namely diluents are not used, and organic solvents such as N-methyl pyrrolidone, N-dimethyl acetamide, N-dimethyl formamide, toluene, xylene, butanone and cyclohexanone are included, so that emission of Volatile Organic Compounds (VOC) is reduced, and environmental friendliness is achieved.
4. Compared with the literature, the invention (1) further solves the problem of agglomeration of graphene and polyaniline, and improves the dispersibility of the phosphated polyaniline-silica graft modified graphene composite material in aqueous resin by anchoring the silica nanoparticles on the surface of the graphene and bonding and grafting the polyaniline with phytic acid; (2) the problem that the synergistic effect of graphene and polyaniline is not ideal is further solved, the polyaniline is grafted by anchoring of the silicon dioxide nano particles on the surface of the graphene and bonding of phytic acid, so that the barrier effect of the 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 problem of organic solvent environmental pollution is solved, the water-based epoxy-containing silicon resin is used as a film forming material of the composite coating, the emission of organic volatile matters is reduced, and environmental friendliness is realized.
Drawings
Fig. 1 is a scanning electron micrograph of the phosphorylated polyaniline-silica graft modified graphene prepared in step two of example 1;
FIG. 2 is a TEM image of the PAA-silica grafted modified graphene prepared in step two of example 1;
FIG. 3 is a photograph of the water contact angle of the coating;
fig. 4 is an electrochemical impedance spectrogram of the phosphated polyaniline-silica graft modified graphene/aqueous epoxy-containing silicon resin composite coating after being soaked in 3.5% NaCl solution for different times;
FIG. 5 is a polarization curve diagram of a phosphated polyaniline-silica graft modified graphene/aqueous epoxy-containing silicon resin composite coating after being soaked in a 3.5% NaCl solution for different times;
fig. 6 is a schematic diagram of an anticorrosion mechanism of the phosphated polyaniline-silicon dioxide graft modified graphene/aqueous epoxy-containing silicon resin composite coating.
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 phosphated polyaniline-silica graft modified graphene/waterborne epoxy-containing silicon resin composite coating comprises the following steps:
firstly, preparing 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 volume of ethyl orthosilicate and the mass of graphene oxide are in a ratio of 50 mL: 1 mg;
the mass fraction of the ammonia water is 25wt%, 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 phosphated polyaniline-silicon dioxide graft modified graphene 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, adding phytic acid, stirring at 100 ℃, performing reflux reaction for 10-12 h, 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 phytic 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 a phosphorized polyaniline-silicon dioxide grafted modified graphene composite material;
the ratio of the volume of the phytic acid to the mass of the graphene oxide in the first step is 50 mL: 1 mg;
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
Ultrasonically dispersing the phosphated polyaniline-silicon dioxide graft modified graphene composite material obtained in the second step in the waterborne epoxy-containing silicon resin obtained in the third step uniformly, coating the mixture on the surface of metal or alloy, and heating and curing the mixture at 50 ℃ to obtain a phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating;
the addition amount of the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the water-based silicone resin is 1.5-3.5 wt.%.
The principle and the beneficial effects of the implementation mode are as follows:
according to the embodiment, the silicon dioxide nano particles are anchored on the surface of graphene, modified by phytic acid and then bonded with the grafted polyaniline to obtain the phosphated polyaniline-silicon dioxide grafted and modified graphene composite material, and the embodiment also provides the aqueous epoxy-containing silicon resin as a film forming material of 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. Meanwhile, the silicon dioxide particles also increase the micro roughness of the surface of the graphene sheet layer, and are beneficial to improving the hydrophobicity of the composite coating.
Secondly, after the phytic acid is modified, phosphate groups in phytic acid 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 phytic acid bonding and grafting composite technology provided by the embodiment can further effectively avoid agglomeration of polyaniline and graphene in a composite coating, so that the dispersibility of the phosphated polyaniline-silicon dioxide graft modified graphene 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 and enhances the conductivity and the electrochemical performance of polyanilineThe chemical activity promotes the passivation effect of polyaniline and metal, accelerates the generation of a passivation film, and further improves the corrosion resistance of the phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating. Compared with the blending composite technology and the non-bonding composite technology of the graphene and the polyaniline, the phytic acid bonding grafting composite technology provided by the embodiment has more obvious synergistic effect on the graphene and the polyaniline.
Fourthly, the phytic acid molecule contains six phosphate groups, and plays multiple roles in the process of modifying the surface of graphene-silicon dioxide, bonding grafted polyaniline and protecting metal from corrosion. Firstly, phytic acid plays a role of a grafting modifier, while part of phosphate groups in phytic acid molecules act on the surface of graphene-silicon dioxide, the other part of phosphate groups are chemically bonded with aniline, so that polyaniline is uniformly covered on the surfaces of silicon dioxide and graphene sheets, and the dispersibility of graphene and polyaniline is further improved; and the phytic acid plays a role of a dopant, and the phytic acid is used as the dopant of the polyaniline, so that the conductivity and the electrochemical activity of the polyaniline can be improved. After the surface of the graphene-silicon dioxide is modified, a large-volume lamellar structure is introduced into the dopant counter ions, so that the barrier property of the polyaniline composite material is improved; thirdly, a plurality of phosphate groups of the phytic acid have a chelating effect with metals, a passivation film can be generated on the metal surface, the passivation effect of polyaniline on the metals is enhanced, and the corrosion resistance of the water-based coating is further improved.
Fifthly, an epoxy group is introduced into the organic silicon resin, and the organic silicon resin is cured to form a film through a three-dimensional network formed by the reaction of the organic silicon resin and the polyaniline-silicon dioxide graft modified graphene composite material, so that the polyaniline-silicon dioxide graft modified graphene/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. However, 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 phosphated polyaniline-silicon dioxide graft modified graphene 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. And the phosphated polyaniline-silicon dioxide grafted modified graphene is uniformly introduced into the silicone resin coating as a curing agent, so that the corrosion resistance of the coating is effectively improved.
Sixth, the phosphated polyaniline-silica graft modified graphene composite material provided by the embodiment has good dispersibility in aqueous resin, realizes the aqueous performance of an anticorrosive coating while improving the anticorrosive performance of the composite coating, and is environment-friendly.
Seventh, the phosphated polyaniline-silica graft modified graphene 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 Mg-Li alloy coated with the coating of the embodiment is only 8.55X 10-9A/cm2The corrosion rate is only 8.82 multiplied by 10-4mm/year. The barrier property and the durability are excellent, and the impedance value of the composite coating can reach 4.06 multiplied by 10 at most9Ω·cm2The impedance value is maintained at 1.51 multiplied by 10 after soaking in 3.5 wt% NaCl solution for 360 hours6Ω·cm2。
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: in the fourth step, the metal is steel.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the fourth step, the alloy is aluminum alloy or magnesium alloy.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes 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 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 the graphene oxide-silicon dioxide composite material.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the second step, the graphene oxide-silicon dioxide composite material obtained in the first step is added into 100mL of deionized water, stirred for 30min to form a dispersion liquid, added with phytic acid, stirred and refluxed for reaction for 11h at 100 ℃, and cooled to room temperature; placing the reflux reaction device in an ice-water bath at 3-5 ℃, adjusting the pH value of a reaction solution to 1 by using phytic 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 phosphorized polyaniline-silicon dioxide grafted modified graphene composite material.
The sixth specific implementation mode is as follows: the difference between this embodiment and one of the first to fifth embodiments is: in the fourth step, the addition amount of the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the aqueous silicone resin is 1.5-3.5 wt.%.
Example 1:
the preparation method of the phosphated polyaniline-silica graft modified graphene/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 volume ratio of the ethyl orthosilicate to the graphene oxide is 50 mL: 1 mg;
the mass fraction of the ammonia water is 25wt%, 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 phosphated polyaniline-silicon dioxide graft modified graphene 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, adding phytic acid, stirring at 100 ℃, performing reflux reaction for 10-12 h, 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 phytic 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 a phosphorized polyaniline-silicon dioxide grafted modified graphene composite material;
the ratio of the volume of the phytic acid to the mass of the graphene oxide in the first step is 50 mL: 1 mg;
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, carrying out surface modification on the graphene oxide-silicon dioxide composite material by adopting phytic acid as a modifier to obtain phytic acid modified silicon dioxide/graphene oxide, introducing an aniline monomer into a dispersion liquid of the phytic acid modified silicon dioxide/graphene oxide, and synthesizing polyaniline on the surface of the graphene-silicon dioxide lamella by utilizing a chemical bonding effect and an in-situ polymerization method to obtain the phosphorized polyaniline-silicon dioxide graft modified graphene 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
Ultrasonically dispersing the phosphated polyaniline-silicon dioxide graft modified graphene composite material obtained in the second step in the waterborne epoxy-containing silicon resin obtained in the third step uniformly, coating the mixture on the surface of a magnesium-lithium (Mg-Li) alloy, and heating and curing the mixture at 50 ℃ to obtain a phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating;
the metal is steel; the alloy is aluminum alloy, magnesium alloy and the like;
the addition amount of the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the water-based silicone resin is 1.5-3.5 wt.%;
and step four, adding the phosphated polyaniline-silicon dioxide graft modified graphene 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 phosphorylated polyaniline-silica graft modified graphene prepared in step two of example 1; as can be seen from fig. 1, polyaniline is uniformly distributed on the surface of the graphene-silica sheet layer, and the agglomeration of polyaniline and graphene in the composite coating is effectively avoided, so that the dispersibility of the phosphated polyaniline-silica graft modified graphene in the aqueous resin is improved.
FIG. 2 is a TEM image of the PAA-silica grafted modified graphene prepared in step two of example 1; as can be seen from fig. 2, graphene with a lamellar structure and silica nanoparticles uniformly distributed on the surface of the lamellar layer are seen, and the surface of graphene-silica is uniformly wrapped by polyaniline, which further proves that the phosphorylated polyaniline-silica graft modified graphene composite material is successfully prepared, and the dispersibility of the graphene lamellar layer and the silica-bonded graft polyaniline is good.
Fig. 3 is a photograph of water contact angle of the coating, which sequentially shows the waterborne epoxy-containing silicone resin coating, the silicon dioxide graft modified graphene/waterborne epoxy-containing silicone resin composite coating, and the phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicone resin composite coating obtained in step three from left to right; the preparation process of the silicon dioxide grafted and modified graphene/waterborne epoxy-containing silicon resin composite coating comprises the following steps: ultrasonically dispersing the graphene-silicon dioxide composite material obtained in the step one in the waterborne epoxy-containing silicon resin obtained in the step three uniformly, coating the graphene-silicon dioxide composite material on the surface of the alloy, and heating and curing at 50 ℃; the three coatings are coated on the surface of a magnesium-lithium (Mg-Li) alloy, and the addition amounts of the silicon dioxide graft modified graphene and the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the aqueous epoxy-containing silicon resin are both 3 wt.%; as can be seen from the water contact angle photograph, the contact angle of the water-based epoxy-containing silicon resin coating can only reach 87 degrees, and when the silicon dioxide modified graphene is used as the functional filler, the nano silicon dioxide particles coated on the surface of the graphene provide hydrophobic micro roughness, so that the water contact angle of the coating reaches 127 degrees. When the phosphated polyaniline-silicon dioxide graft modified graphene is added into the silicon resin coating, the hydrophobicity of the coating is the best, and the water contact angle reaches 151 degrees.
Fig. 4 is an electrochemical impedance spectrogram of the phosphated polyaniline-silica graft modified graphene/aqueous epoxy-containing silicon resin composite coating after being soaked in 3.5% NaCl solution for different times; at the initial stage of soaking (0h), the phosphated polyaniline-silicon dioxide is grafted and modifiedThe impedance value of the composite coating of the graphene/the water-based epoxy-containing silicon resin reaches 4.06 multiplied by 109Ω·cm2The method proves that the phosphated polyaniline-silicon dioxide graft modified graphene enables the blocking effect of the graphene and the passivation effect of the polyaniline to be better and synergistically exerted, and the corrosion resistance of the composite coating is remarkably improved. 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 the coating and permeates into the surface of the alloy. However, after the coating is soaked for 360 hours, the impedance value of the phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating can still reach 1.51 multiplied by 106Ω·cm2The phosphated polyaniline-silicon dioxide grafted modified graphene/waterborne epoxy-containing silicon resin composite coating has better durability, and the alloy can obtain long-term corrosion protection due to the good barrier property and electrochemical protection property of the phosphated polyaniline-silicon dioxide grafted modified graphene/waterborne epoxy-containing silicon resin composite coating.
Fig. 5 is a polarization curve diagram of the phosphated polyaniline-silica graft modified graphene/aqueous epoxy-containing silicon resin composite coating after being soaked in 3.5% NaCl solution for different times. At the initial stage of soaking (0h), the corrosion current density of the phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating is 8.55 multiplied by 10-9A/cm2The corrosion rate is 8.16 multiplied by 10-5mm/year, the corrosion current density and the corrosion rate are increased along with the prolonging of the soaking time, but after the soaking time is 360 hours, the corrosion current density of the phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating is still only 9.53 multiplied by 10-8A/cm2The corrosion rate is 2.52 multiplied by 10-3mm/year, the coating shows better corrosion resistance and better durability.
Fig. 6 is a schematic diagram of an anticorrosion mechanism of the phosphated polyaniline-silicon dioxide graft modified graphene/aqueous epoxy-containing silicon resin composite coating. The phytic acid is adopted to chemically bond and graft polyaniline on the surface of the graphene-silicon dioxide, so that the polyaniline is uniformly coated on the surface of the graphene-silicon dioxide, the dispersity of the polyaniline in the water-based silicon resin is improved, the uniformly dispersed phosphated polyaniline-silicon dioxide graft modified graphene prolongs the diffusion path of a corrosive medium, and the synergistic effect of the graphene and the polyaniline is enhanced. The blocking capability of the graphene sheet layer is improved by the polyaniline, the electrochemical activity of the polyaniline is enhanced by the graphene, the passivation effect of the polyaniline and the alloy is promoted, and the generation of a passivation film is further accelerated by the phytic acid, so that the corrosion resistance is improved.

Claims (5)

1. A preparation method of a phosphated polyaniline-silicon dioxide graft modified graphene/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 volume ratio of the ethyl orthosilicate to the graphene oxide is 50 mL: 1 mg;
the mass fraction of the ammonia water is 25wt%, 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 phosphated polyaniline-silicon dioxide graft modified graphene 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, adding phytic acid, stirring at 100 ℃, performing reflux reaction for 10-12 h, 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 phytic 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 a phosphorized polyaniline-silicon dioxide grafted modified graphene composite material;
the ratio of the volume of the phytic acid to the mass of the graphene oxide in the first step is 50 mL: 1 mg;
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 waterborne epoxy-containing silicon 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
Ultrasonically dispersing the phosphated polyaniline-silicon dioxide graft modified graphene composite material obtained in the second step in the waterborne epoxy-containing silicon resin obtained in the third step uniformly, coating the mixture on the surface of metal, and heating and curing at 50 ℃ to obtain a phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating;
the addition amount of the phosphated polyaniline-silicon dioxide graft modified graphene composite material in the aqueous epoxy-containing silicon resin is 1.5-3.5 wt.%.
2. The preparation method of the phosphated polyaniline-silica graft modified graphene/aqueous epoxy-containing silicon resin composite coating according to claim 1, wherein the preparation method comprises the following steps: in the fourth step, the metal is steel.
3. The preparation method of the phosphated polyaniline-silica graft modified graphene/aqueous epoxy-containing silicon resin composite coating according to claim 1, wherein the preparation method comprises the following steps: in the fourth step, the metal is aluminum alloy or magnesium alloy.
4. The preparation method of the phosphated polyaniline-silica graft modified graphene/aqueous epoxy-containing silicon resin composite coating according to claim 1, wherein the preparation method comprises the following steps: 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 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 the graphene oxide-silicon dioxide composite material.
5. The preparation method of the phosphated polyaniline-silica graft modified graphene/aqueous epoxy-containing silicon resin composite coating according to claim 1, wherein the preparation method comprises the following steps: 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, adding phytic acid, stirring at 100 ℃, performing reflux reaction for 11h, and cooling to room temperature; placing the reflux reaction device in an ice-water bath at 3-5 ℃, adjusting the pH value of a reaction solution to 1 by using phytic 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 phosphorized polyaniline-silicon dioxide grafted modified graphene composite material.
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