CN115637095A - Modified graphene water-based anticorrosive paint and preparation method thereof - Google Patents
Modified graphene water-based anticorrosive paint and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of coatings, and particularly relates to a modified graphene water-based anticorrosive coating and a preparation method thereof. The anticorrosive paint comprises the following raw materials in parts by weight: 55-65 parts of water-based epoxy resin; 4-8 parts of octadecylamine and silane co-modified graphene oxide and 2-4 parts of silane modified zinc-copper-iron hydrotalcite; 15-25 parts of a diluent; 8-16 parts of a curing agent; 3-7 parts of a dispersing agent and 3-5 parts of a defoaming agent; 3-5 parts of a coupling agent. The modified graphene water-based anticorrosive coating prepared by the invention has excellent anticorrosive performance and mechanical performance.
Description
Technical Field
The invention belongs to the technical field of coatings. More particularly, relates to a modified graphene water-based anticorrosive paint and a preparation method thereof.
Background
The aqueous epoxy resin is an emulsion in which an epoxy resin is dispersed in water by an appropriate method, the water serves as a continuous phase, the epoxy resin is present in the form of fine particles or droplets in the water, and the two are mixed to form a stable dispersion. The waterborne epoxy resin not only keeps the original advantages of the epoxy resin, but also has the advantages of good environmental protection performance, low price, simple, convenient and safe transportation and storage, simple construction, easy cleaning and the like. However, the water-based epoxy coating is brittle and has poor corrosion resistance, so that the modification of the water-based epoxy coating to obtain a high-performance anticorrosive coating is a great hot spot of the current research.
Conductive polymer and nano filler are added into the epoxy resin matrix, so that the electrostatic conductivity of the coating can be improved, the formation of a metal/polymer interface passivation layer can be promoted, and the nano composite coating is a physical barrier capable of effectively preventing corrosive ions from permeating. Similarly, inorganic nanoparticles such as carbon nanotubes, silicon dioxide, boron nitride and Graphene (GO) are introduced into organic chain segments such as epoxy-polyamide, so that the properties of the nanocomposite coating such as barrier property, adhesive force, wear resistance, corrosion resistance and thermal stability can be improved. The nano modification can also endow the coating with other special properties, and has wide application prospects in the fields of aerospace, electronic equipment, automobiles, buildings, biomedicine and the like.
Lin Shen and the like add graphene nanofillers into an epoxy resin system to obtain a series of epoxy group nanocomposite materials, a Molecular Dynamics (MD) simulation method is adopted to establish a composite model of epoxy resin and 4 graphene nanosheets (unmodified, carboxyl functionalized, amino functionalized and hydroxyl functionalized), and physical properties such as dielectric constant, thermal conductivity, mechanical properties, glass transition temperature and the like of the nanocomposite materials are researched. The result shows that the physical properties of the polymer can be improved to different degrees by doping the graphene nanosheets. The dielectric constant of the epoxy resin (EP-GNOH) doped by the hydroxyl functionalized graphene nanosheet is reduced by 25.9%, and the EPGNOH hybrid coating can effectively inhibit the accumulation of surface charges. And epoxy resin (EP-GNNH) doped with amino functionalized graphene nanosheets 2 ) Only the thermal conductivity is increased by 44.86 percent, and other physical properties are not obviously improved.
CN111253782B discloses modified anticorrosive hydrotalcite, a water-based intelligent anticorrosive coating, a preparation method and a coating, wherein the preparation method of the modified anticorrosive hydrotalcite comprises the following steps: dripping a mixed solution of a metal nitrate solution, sodium hydroxide and sodium tripolyphosphate into deionized water, stirring and centrifuging to obtain anticorrosive hydrotalcite; and adding the anticorrosive hydrotalcite and dopamine into a buffer solution, stirring and centrifuging to obtain the modified anticorrosive hydrotalcite. According to the invention, the corrosion resistance is improved by utilizing the capability of the tripolyphosphate ions to passivate metal to form a protective film and the lamellar blocking effect of the hydrotalcite, the coating made of the modified corrosion-resistant hydrotalcite is coated on the surface of steel, and when the steel is corroded to generate metal cations, the catechol group on the dopamine and the metal cations can form a cross-linked network structure, so that the coating is adsorbed on the surface of a steel matrix, and the effects of automatic protection and intelligent corrosion prevention are achieved.
CN113174183B discloses an organic solvent-free graphene-reinforced aqueous epoxy resin coating and a preparation method thereof, wherein an acrylic ester is introduced onto a molecular chain of an emulsifier to prepare a cationic aqueous epoxy resin emulsifier, and the cationic aqueous epoxy resin emulsifier is mixed with a low molecular weight epoxy resin and graphene to prepare the graphene-reinforced aqueous epoxy resin coating. In the process, amino and ionic sites can be introduced by using the methylene bisacrylamide, and then an acrylate monomer is introduced through free radical polymerization and enters an emulsifier molecular chain, and the dispersion stability of the emulsion is improved by introducing a polypropylene glycol chain segment. The invention solves the problems of uncontrollable emulsifier synthesis process, large viscosity, uneven reaction, influence on water resistance and the like, solves the limitation that an organic solvent must be added in emulsifier synthesis, realizes the purpose of preparing the emulsifier without any volatile organic solvent, and the obtained graphene reinforced water-based epoxy resin coating has excellent mechanical property and corrosion resistance.
In summary, the addition of inorganic substances such as graphene to the aqueous epoxy resin coating to improve the corrosion resistance and mechanical properties of the coating has led to certain success, but the requirements of actual production cannot be met.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a modified graphene water-based anticorrosive paint and a preparation method thereof. The anticorrosive paint comprises the following raw materials in parts by weight: 55-65 parts of waterborne epoxy resin; 4-8 parts of octadecylamine and silane co-modified graphene oxide and 2-4 parts of silane modified zinc-copper-iron hydrotalcite; 15-25 parts of a diluent; 8-16 parts of a curing agent; 3-7 parts of a dispersing agent and 3-5 parts of a defoaming agent; 3-5 parts of a coupling agent. The modified graphene water-based anticorrosive coating prepared by the invention has excellent anticorrosive performance and mechanical performance.
The invention aims to provide a modified graphene water-based anticorrosive paint.
The invention also aims to provide a preparation method of the modified graphene water-based anticorrosive paint.
The above purpose of the invention is realized by the following technical scheme:
the modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
55-65 parts of water-based epoxy resin; 4-8 parts of octadecylamine and silane co-modified graphene oxide and 2-4 parts of silane modified zinc-copper-iron hydrotalcite; 15-25 parts of a diluent; 8-16 parts of a curing agent; 3-7 parts of a dispersing agent and 3-5 parts of a defoaming agent; 3-5 parts of a coupling agent.
Preferably, the preparation method of the octadecylamine and silane coupling agent co-modified graphene oxide comprises the following steps:
adding graphene oxide into an ethanol solution containing octadecylamine and a silane coupling agent for reaction, and then centrifuging, washing and drying to obtain the octadecylamine and silane co-modified graphene oxide.
Preferably, the silane coupling agent is at least one of KH550, KH560 and KH 570.
Preferably, the mass ratio of the graphene oxide to the octadecylamine and the silane coupling agent is 1:0.1 to 0.3; the reaction is carried out for 12 to 18 hours at a temperature of between 60 and 80 ℃; the drying is carried out for 10 to 18 hours at the temperature of between 80 and 120 ℃.
Preferably, the preparation method of the silane modified zinc-copper-iron hydrotalcite comprises the following steps: (a) Weighing copper salt, zinc salt and iron salt, dissolving the copper salt, the zinc salt and the iron salt in deionized water to prepare a mixed salt solution, stirring, then dropwise adding alkali liquor to adjust the pH of the solution, then transferring the solution to a hydrothermal reaction kettle for reaction, centrifuging, washing, drying and grinding to obtain zinc-copper-iron hydrotalcite; (b) And (b) adding the zinc-copper-iron hydrotalcite obtained in the step (a) into a silane coupling agent ethanol solution for reaction, and then centrifuging, washing and drying to obtain the silane modified zinc-copper-iron hydrotalcite.
Preferably, in step (a); the stirring time is 20-40 min, and the pH value is 9-11; the hydrothermal reaction is carried out for 10 to 16 hours at a temperature of between 120 and 140 ℃; the drying is carried out for 14 to 20 hours at a temperature of between 80 and 120 ℃.
Preferably, in step (b); the concentration of the ethanol solution of the silane coupling agent is 2-4 mol/L; the reaction is carried out for 5 to 9 hours at a temperature of between 60 and 80 ℃; the drying is carried out for 14 to 20 hours at a temperature of between 80 and 100 ℃.
Preferably, the copper salt is at least one of copper acetate, copper chloride and copper nitrate; the zinc salt is at least one of zinc nitrate, zinc acetate and zinc chloride; the ferric salt is at least one of ferric nitrate, ferric chloride and ferric acetate; the alkali is sodium carbonate and sodium hydroxide.
Preferably, the molar ratio of sodium carbonate to sodium hydroxide is 1:0.2 to 0.4.
Preferably, in the step (a), the molar ratio of copper, zinc and iron is 1:1:2-4: the concentration of the alkali liquor is 2-4 mol/L.
Preferably, in the step (b), the molar ratio of copper to silane is 1; the silane is at least one of KH550, KH560 and KH 570.
Preferably, the diluent is water; the curing agent is at least one of waterborne epoxy curing agent EA-15, waterborne epoxy curing agent EA-31 and waterborne epoxy curing agent H202B; the dispersant is at least one of BYK-180, BYK-190 and BYK-192; the defoaming agent is at least one of BYK-019, BYK-024 and BYK-028; the coupling agent is at least one of KH550, KH560 and KH 570.
The preparation method of the modified graphene water-based anticorrosive coating comprises the following steps of firstly mixing the water-based epoxy resin, octadecylamine and silane co-modified graphene oxide, the silane modified zinc-copper-iron hydrotalcite and the diluent in a high-speed mixer at a stirring speed of 3000-4000 r/min for 20-60 min, then adding the curing agent, the dispersing agent, the defoaming agent and the coupling agent into the mixture, and continuously stirring for 20-40 min to obtain the anticorrosive coating.
The invention has the following beneficial effects:
(1) According to the invention, the octadecylamine and silane co-modified graphene oxide is adopted, so that the dispersibility of the graphene oxide in the coating is improved, and the corrosion resistance and mechanical properties of the coating are also improved.
(2) The silane modified zinc-copper-iron hydrotalcite improves the dispersibility of the zinc-copper-iron hydrotalcite in the coating, and further improves the corrosion resistance and mechanical properties of the anticorrosive coating.
(3) The preparation method has the advantages of simple preparation process, rich raw material sources, low price and excellent application prospect.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
The modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
60 parts of water-based epoxy resin; 6 parts of octadecylamine and silane co-modified graphene oxide and 3 parts of silane modified zinc-copper-iron hydrotalcite; 20 parts of a diluent; 12 parts of a curing agent; 5 parts of a dispersing agent and 4 parts of a defoaming agent; 4 parts of a coupling agent;
the preparation method of the silane modified zinc-copper-iron hydrotalcite comprises the following steps:
(a) Weighing 1mol of copper acetate, 1mol of zinc nitrate and 3mol of ferric nitrate, dissolving the copper acetate, the 1mol of zinc nitrate and the 3mol of ferric nitrate in 50mL of deionized water to prepare a mixed salt solution, stirring for 30min, then dropwise adding a mixed alkali solution of sodium carbonate and sodium hydroxide (wherein the molar ratio of the sodium carbonate to the sodium hydroxide is 1.3, and the concentration of the alkali solution is 3 mol/L), adjusting the pH =10 of the solution, and then transferring the solution to a hydrothermal reaction kettle for reaction, wherein the hydrothermal reaction is carried out at 130 ℃ for 13h; centrifuging, washing, drying at 100 ℃ for 18h, and grinding to obtain zinc-copper-iron hydrotalcite;
(b) And (b) adding the zinc-copper-iron hydrotalcite obtained in the step (a) into 50mL of 4mol/L KH560 ethanol solution, reacting for 7h at 70 ℃, centrifuging, washing, and drying for 18h at 90 ℃ to obtain the silane modified zinc-copper-iron hydrotalcite.
The preparation method of the octadecylamine and silane coupling agent co-modified graphene oxide comprises the following steps:
adding 1g of graphene oxide into 50mL of ethanol solution containing octadecyl amine and KH560 (wherein the mass concentration of octadecyl amine is 6g/L and the mass concentration of KH560 is 4 g/L) to react at 70 ℃ for 15h, centrifuging, washing, and drying at 100 ℃ for 14h to obtain the octadecyl amine and silane co-modified graphene oxide.
The diluent is water;
the curing agent is a waterborne epoxy curing agent EA-15;
the dispersant is BYK-180;
the defoaming agent is BYK-019;
the coupling agent is KH550;
a preparation method of a modified graphene water-based anticorrosive coating comprises the following steps of firstly putting water-based epoxy resin, octadecylamine, silane co-modified graphene oxide, silane modified zinc-copper-iron hydrotalcite and a diluent into a high-speed stirrer to be mixed, wherein the stirring speed is 3500r/min, stirring for 40min, then adding a curing agent, a dispersing agent, an antifoaming agent and a coupling agent into the mixture, and continuously stirring for 30min to obtain the anticorrosive coating.
Example 2
The modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
65 parts of water-based epoxy resin; 4 parts of octadecylamine and silane co-modified graphene oxide and 4 parts of silane modified zinc-copper-iron hydrotalcite; 15 parts of a diluent; 16 parts of a curing agent; 3 parts of a dispersing agent and 5 parts of a defoaming agent; 3 parts of a coupling agent;
the preparation method of the silane modified zinc-copper-iron hydrotalcite comprises the following steps:
(a) Weighing 1mol of copper chloride, 1mol of zinc acetate and 4mol of ferric chloride, dissolving the copper chloride, the 1mol of zinc acetate and the 4mol of ferric chloride in 50mL of deionized water to prepare a mixed salt solution, stirring for 40min, then dropwise adding a mixed alkali solution of sodium carbonate and sodium hydroxide (wherein the molar ratio of the sodium carbonate to the sodium hydroxide is 1:0.3, and the concentration of the alkali solution is 3 mol/L), adjusting the pH =11 of the solution, then transferring the solution to a hydrothermal reaction kettle for reaction, wherein the hydrothermal reaction comprises the steps of reacting at 140 ℃ for 10h, centrifuging, washing, drying at 120 ℃ for 14h, and grinding to obtain zinc-copper-iron hydrotalcite;
(b) And (b) adding the zinc-copper-iron hydrotalcite obtained in the step (a) into 100mL of 3mol/L KH550 ethanol solution, reacting for 5h at 80 ℃, centrifuging, washing, and drying for 14h at 100 ℃ to obtain the silane modified zinc-copper-iron hydrotalcite.
The preparation method of the octadecylamine and silane coupling agent co-modified graphene oxide comprises the following steps:
adding 1g of graphene oxide into 50mL of ethanol solution containing octadecylamine and KH550 (wherein the mass concentration of the octadecylamine is 8g/L, and the mass concentration of the KH550 is 2 g/L), reacting at 80 ℃ for 12h, centrifuging, washing, and drying at 120 ℃ for 10h to obtain the octadecylamine and silane co-modified graphene oxide.
The diluent is water;
the curing agent is a waterborne epoxy curing agent EA-31;
the dispersant is BYK-190;
the defoaming agent is BYK-024;
the coupling agent is KH560;
a preparation method of a modified graphene water-based anticorrosive coating comprises the following steps of firstly putting water-based epoxy resin, octadecylamine, silane co-modified graphene oxide, silane modified zinc-copper-iron hydrotalcite and a diluent into a high-speed stirrer to be mixed, stirring for 20min at the stirring speed of 4000r/min, then adding a curing agent, a dispersing agent, an antifoaming agent and a coupling agent into the mixture, and continuously stirring for 40min to obtain the anticorrosive coating.
Example 3
The modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
55 parts of water-based epoxy resin; 8 parts of octadecylamine and silane co-modified graphene oxide and 2 parts of silane modified zinc-copper-iron hydrotalcite; 25 parts of a diluent; 8 parts of a curing agent; 7 parts of a dispersing agent and 3 parts of a defoaming agent; 5 parts of a coupling agent;
the preparation method of the silane modified zinc-copper-iron hydrotalcite comprises the following steps:
(a) Weighing 1mol of copper nitrate, 1mol of zinc chloride and 2mol of ferric chloride, dissolving the copper nitrate, the zinc chloride and the ferric chloride in 50mL of deionized water to prepare a mixed salt solution, stirring for 20min, then dropwise adding a mixed alkali solution of sodium carbonate and sodium hydroxide (wherein the molar ratio of the sodium carbonate to the sodium hydroxide is 1.3, and the concentration of the alkali solution is 3 mol/L), adjusting the pH =9 of the solution, then transferring the solution to a hydrothermal reaction kettle, reacting for 16h at 120 ℃, centrifuging, washing, drying for 20h at 80 ℃, and grinding to obtain zinc-copper-iron hydrotalcite;
(b) And (b) adding the zinc-copper-iron hydrotalcite obtained in the step (a) into 50mL of 2mol/L KH570 ethanol solution, reacting at 60 ℃ for 9h, centrifuging, washing, and drying at 80 ℃ for 20h to obtain the silane modified zinc-copper-iron hydrotalcite.
The preparation method of the octadecylamine and silane coupling agent co-modified graphene oxide comprises the following steps:
1g of graphene oxide is added into 50mL of ethanol solution containing octadecylamine and KH570 (wherein the mass concentration of the octadecylamine is 4g/L, and the mass concentration of the KH570 is 6 g/L) to react at 60 ℃ for 18h, and then the graphene oxide co-modified by the octadecylamine and silane is obtained by centrifuging, washing and drying at 80 ℃ for 18h.
The diluent is water;
the curing agent is a water-based epoxy curing agent H202B;
the dispersant is BYK-192;
the defoaming agent is BYK-028;
the coupling agent is KH570;
a preparation method of a modified graphene water-based anticorrosive coating comprises the following steps of firstly putting water-based epoxy resin, octadecylamine, silane co-modified graphene oxide, silane modified zinc-copper-iron hydrotalcite and a diluent into a high-speed stirrer to be mixed, stirring for 60min at a stirring speed of 3000r/min, then adding a curing agent, a dispersing agent, an antifoaming agent and a coupling agent into the mixture, and continuously stirring for 20min to obtain the anticorrosive coating.
Comparative example 1
The modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
60 parts of water-based epoxy resin; 6 parts of octadecylamine modified graphene oxide and 3 parts of silane modified zinc-copper-iron hydrotalcite; 20 parts of a diluent; 12 parts of a curing agent; 5 parts of a dispersing agent and 4 parts of a defoaming agent; 4 parts of a coupling agent;
the preparation method of the silane modified zinc-copper-iron hydrotalcite comprises the following steps:
(a) Weighing 1mol of copper acetate, 1mol of zinc nitrate and 3mol of ferric nitrate, dissolving the copper acetate, the 1mol of zinc nitrate and the 3mol of ferric nitrate in 50mL of deionized water to prepare a mixed salt solution, stirring for 30min, then dropwise adding a mixed alkali solution of sodium carbonate and sodium hydroxide (wherein the molar ratio of the sodium carbonate to the sodium hydroxide is 1.3, and the concentration of the alkali solution is 3 mol/L), adjusting the pH =10 of the solution, and then transferring the solution to a hydrothermal reaction kettle for reaction, wherein the hydrothermal reaction is carried out at 130 ℃ for 13h; centrifuging, washing, drying at 100 ℃ for 18h, and grinding to obtain zinc-copper-iron hydrotalcite;
(b) And (b) adding the zinc-copper-iron hydrotalcite obtained in the step (a) into 50mL of 4mol/L KH560 ethanol solution, reacting for 7h at 70 ℃, centrifuging, washing, and drying for 18h at 90 ℃ to obtain the silane modified zinc-copper-iron hydrotalcite.
The preparation method of the octadecylamine and silane coupling agent co-modified graphene oxide comprises the following steps:
adding 1g of graphene oxide into 50mL of ethanol solution containing octadecylamine (wherein the mass concentration of the octadecylamine is 10 g/L), reacting for 15h at 70 ℃, centrifuging, washing, and drying for 14h at 100 ℃ to obtain the octadecylamine and silane co-modified graphene oxide.
The diluent is water;
the curing agent is a waterborne epoxy curing agent EA-15;
the dispersant is BYK-180;
the defoaming agent is BYK-019;
the coupling agent is KH550;
a preparation method of a modified graphene water-based anticorrosive coating comprises the following steps of firstly mixing water-based epoxy resin, octadecylamine modified graphene oxide, silane modified zinc-copper-iron hydrotalcite and a diluent in a high-speed mixer at a mixing speed of 3500r/min for 40min, then adding a curing agent, a dispersing agent, an antifoaming agent and a coupling agent into the mixture, and continuously stirring for 30min to obtain the anticorrosive coating.
Comparative example 2
The modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
60 parts of water-based epoxy resin; 6 parts of silane modified graphene oxide and 3 parts of silane modified zinc-copper-iron hydrotalcite; 20 parts of a diluent; 12 parts of a curing agent; 5 parts of a dispersing agent and 4 parts of a defoaming agent; 4 parts of a coupling agent;
the preparation method of the silane modified zinc-copper-iron hydrotalcite comprises the following steps:
(a) Weighing 1mol of copper acetate, 1mol of zinc nitrate and 3mol of ferric nitrate, dissolving the copper acetate, the 1mol of zinc nitrate and the 3mol of ferric nitrate in 50mL of deionized water to prepare a mixed salt solution, stirring for 30min, then dropwise adding a mixed alkali solution of sodium carbonate and sodium hydroxide (wherein the molar ratio of the sodium carbonate to the sodium hydroxide is 1.3, and the concentration of the alkali solution is 3 mol/L), adjusting the pH =10 of the solution, and then transferring the solution to a hydrothermal reaction kettle for reaction, wherein the hydrothermal reaction is carried out at 130 ℃ for 13h; centrifuging, washing, drying at 100 ℃ for 18h, and grinding to obtain zinc-copper-iron hydrotalcite;
(b) And (b) adding the zinc-copper-iron hydrotalcite obtained in the step (a) into 50mL of 4mol/L KH560 ethanol solution, reacting for 7 hours at 70 ℃, centrifuging, washing, and drying for 18 hours at 90 ℃ to obtain the silane-modified zinc-copper-iron hydrotalcite.
The preparation method of the silane coupling agent modified graphene oxide comprises the following steps:
adding 1g of graphene oxide into 50mL of ethanol solution containing KH560 (wherein the mass concentration of KH560 is 10 g/L), reacting at 70 ℃ for 15h, centrifuging, washing, and drying at 100 ℃ for 14h to obtain octadecylamine and silane co-modified graphene oxide.
The diluent is water;
the curing agent is a waterborne epoxy curing agent EA-15;
the dispersant is BYK-180;
the defoaming agent is BYK-019;
the coupling agent is KH550;
the preparation method of the modified graphene water-based anticorrosive coating comprises the following steps of firstly putting the water-based epoxy resin, the silane co-modified graphene oxide, the silane modified zinc-copper-iron hydrotalcite and the diluent into a high-speed stirrer to be mixed, stirring at a speed of 3500r/min for 40min, then adding the curing agent, the dispersing agent, the defoaming agent and the coupling agent into the mixture, and continuously stirring for 30min to obtain the anticorrosive coating.
Comparative example 3
The modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
60 parts of water-based epoxy resin; 6 parts of octadecylamine and silane co-modified graphene oxide and 3 parts of silane modified copper-iron hydrotalcite; 20 parts of a diluent; 12 parts of a curing agent; 5 parts of a dispersing agent and 4 parts of a defoaming agent; 4 parts of a coupling agent;
the preparation method of the silane modified copper-iron hydrotalcite comprises the following steps:
(a) Weighing 2mol of copper acetate and 3mol of ferric nitrate, dissolving the copper acetate and the ferric nitrate in 50mL of deionized water to prepare a mixed salt solution, stirring for 30min, then dropwise adding a mixed alkali solution of sodium carbonate and sodium hydroxide (wherein the molar ratio of the sodium carbonate to the sodium hydroxide is 1.3, and the concentration of the alkali solution is 3 mol/L), adjusting the pH of the solution to be =10, and then transferring the solution to a hydrothermal reaction kettle for reaction, wherein the hydrothermal reaction is carried out at 130 ℃ for 13h; centrifuging, washing, drying at 100 ℃ for 18h, and grinding to obtain copper-iron hydrotalcite;
(b) And (b) adding the copper-iron hydrotalcite obtained in the step (a) into 50mL of 4mol/L KH560 ethanol solution, reacting for 7 hours at 70 ℃, centrifuging, washing, and drying for 18 hours at 90 ℃ to obtain the silane modified copper-iron hydrotalcite.
The preparation method of the octadecylamine and silane coupling agent co-modified graphene oxide comprises the following steps:
adding 1g of graphene oxide into 50mL of ethanol solution containing octadecyl amine and KH560 (wherein the mass concentration of octadecyl amine is 6g/L and the mass concentration of KH560 is 4 g/L) to react at 70 ℃ for 15h, centrifuging, washing, and drying at 100 ℃ for 14h to obtain the octadecyl amine and silane co-modified graphene oxide.
The diluent is water;
the curing agent is a waterborne epoxy curing agent EA-15;
the dispersant is BYK-180;
the defoaming agent is BYK-019; the coupling agent is KH550;
the preparation method comprises the following steps of firstly putting the waterborne epoxy resin, octadecylamine, silane co-modified graphene oxide, silane modified copper-iron hydrotalcite and a diluent into a high-speed stirrer to be mixed, stirring at the speed of 3500r/min for 40min, then adding the curing agent, the dispersing agent, the defoaming agent and the coupling agent into the mixture, and continuously stirring for 30min to obtain the anticorrosive coating.
Comparative example 4
The modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
60 parts of water-based epoxy resin; 6 parts of octadecylamine and silane co-modified graphene oxide and 3 parts of silane modified zinc-iron hydrotalcite; 20 parts of a diluent; 12 parts of a curing agent; 5 parts of a dispersing agent and 4 parts of a defoaming agent; 4 parts of a coupling agent;
the preparation method of the silane modified zinc-copper-iron hydrotalcite comprises the following steps:
(a) Weighing 2mol of zinc nitrate and 3mol of ferric nitrate, dissolving the zinc nitrate and the ferric nitrate in 50mL of deionized water to prepare a mixed salt solution, stirring for 30min, then dropwise adding a mixed alkali solution of sodium carbonate and sodium hydroxide (wherein the molar ratio of the sodium carbonate to the sodium hydroxide is 1.3, and the concentration of the alkali solution is 3 mol/L), adjusting the pH =10 of the solution, and then transferring the solution to a hydrothermal reaction kettle for reaction, wherein the hydrothermal reaction is carried out at 130 ℃ for 13h; centrifuging, washing, drying at 100 ℃ for 18h, and grinding to obtain zinc-iron hydrotalcite;
(b) And (b) adding the zinc-iron hydrotalcite obtained in the step (a) into 50mL of 4mol/L KH560 ethanol solution, reacting for 7 hours at 70 ℃, centrifuging, washing, and drying for 18 hours at 90 ℃ to obtain the silane-modified zinc-iron hydrotalcite.
The preparation method of the octadecylamine and silane coupling agent co-modified graphene oxide comprises the following steps:
adding 1g of graphene oxide into 50mL of ethanol solution containing octadecylamine and KH560 (wherein the mass concentration of the octadecylamine is 6g/L and the mass concentration of the KH560 is 4 g/L) to react for 15h at 70 ℃, centrifuging, washing, and drying for 14h at 100 ℃ to obtain the octadecylamine and silane co-modified graphene oxide.
The diluent is water;
the curing agent is a waterborne epoxy curing agent EA-15;
the dispersant is BYK-180;
the defoaming agent is BYK-019; the coupling agent is KH550;
the preparation method comprises the following steps of firstly putting the waterborne epoxy resin, octadecylamine, silane co-modified graphene oxide, silane modified zinc-iron hydrotalcite and a diluent into a high-speed stirrer to be mixed, stirring at the speed of 3500r/min for 40min, then adding the curing agent, the dispersing agent, the defoaming agent and the coupling agent into the mixture, and continuously stirring for 30min to obtain the anticorrosive coating.
Comparative example 5
The modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
60 parts of water-based epoxy resin; 6 parts of octadecylamine and silane co-modified graphene oxide and 3 parts of zinc-copper-iron hydrotalcite; 20 parts of a diluent; 12 parts of a curing agent; 5 parts of a dispersing agent and 4 parts of a defoaming agent; 4 parts of a coupling agent;
the preparation method of the zinc-copper-iron hydrotalcite comprises the following steps:
weighing 1mol of copper acetate, 1mol of zinc nitrate and 3mol of ferric nitrate, dissolving the copper acetate, the 1mol of zinc nitrate and the 3mol of ferric nitrate in 50mL of deionized water to prepare a mixed salt solution, stirring for 30min, then dropwise adding a mixed alkali solution of sodium carbonate and sodium hydroxide (wherein the molar ratio of the sodium carbonate to the sodium hydroxide is 1.3, and the concentration of the alkali solution is 3 mol/L), adjusting the pH =10 of the solution, and then transferring the solution to a hydrothermal reaction kettle for reaction, wherein the hydrothermal reaction is carried out at 130 ℃ for 13h; centrifuging, washing, drying at 100 deg.C for 18h, and grinding to obtain zinc-copper-iron hydrotalcite.
The preparation method of the octadecylamine and silane coupling agent co-modified graphene oxide comprises the following steps:
adding 1g of graphene oxide into 50mL of ethanol solution containing octadecyl amine and KH560 (wherein the mass concentration of octadecyl amine is 6g/L and the mass concentration of KH560 is 4 g/L) to react at 70 ℃ for 15h, centrifuging, washing, and drying at 100 ℃ for 14h to obtain the octadecyl amine and silane co-modified graphene oxide.
The diluent is water;
the curing agent is a waterborne epoxy curing agent EA-15;
the dispersant is BYK-180;
the defoaming agent is BYK-019; the coupling agent is KH550;
a preparation method of a modified graphene water-based anticorrosive coating comprises the following steps of firstly putting water-based epoxy resin, octadecylamine, silane co-modified graphene oxide, zinc-copper-iron hydrotalcite and a diluent into a high-speed stirrer to be mixed, wherein the stirring speed is 3500r/min, stirring for 40min, then adding a curing agent, a dispersing agent, an antifoaming agent and a coupling agent into the mixture, and continuously stirring for 30min to obtain the anticorrosive coating.
Comparative example 6
The modified graphene water-based anticorrosive paint comprises the following raw materials in parts by weight:
60 parts of water-based epoxy resin; 6 parts of graphene oxide and 3 parts of silane modified zinc-copper-iron hydrotalcite; 20 parts of a diluent; 12 parts of a curing agent; 5 parts of a dispersing agent and 4 parts of a defoaming agent; 4 parts of a coupling agent;
the preparation method of the silane modified zinc-copper-iron hydrotalcite comprises the following steps:
(a) Weighing 1mol of copper acetate, 1mol of zinc nitrate and 3mol of ferric nitrate, dissolving the copper acetate, the 1mol of zinc nitrate and the 3mol of ferric nitrate in 50mL of deionized water to prepare a mixed salt solution, stirring for 30min, then dropwise adding a mixed alkali solution of sodium carbonate and sodium hydroxide (wherein the molar ratio of the sodium carbonate to the sodium hydroxide is 1.3, and the concentration of the alkali solution is 3 mol/L), adjusting the pH =10 of the solution, and then transferring the solution to a hydrothermal reaction kettle for reaction, wherein the hydrothermal reaction is carried out at 130 ℃ for 13h; centrifuging, washing, drying at 100 ℃ for 18h, and grinding to obtain zinc-copper-iron hydrotalcite;
(b) And (b) adding the zinc-copper-iron hydrotalcite obtained in the step (a) into 50mL of 4mol/L KH560 ethanol solution, reacting for 7h at 70 ℃, centrifuging, washing, and drying for 18h at 90 ℃ to obtain the silane modified zinc-copper-iron hydrotalcite.
The diluent is water;
the curing agent is a waterborne epoxy curing agent EA-15;
the dispersant is BYK-180;
the defoaming agent is BYK-019; the coupling agent is KH550;
the preparation method of the modified graphene water-based anticorrosive coating comprises the following steps of firstly putting the water-based epoxy resin, the graphene oxide, the silane modified zinc-copper-iron hydrotalcite and the diluent into a high-speed stirrer to be mixed, stirring at a speed of 3500r/min for 40min, then adding the curing agent, the dispersing agent, the defoaming agent and the coupling agent into the mixture, and continuously stirring for 30min to obtain the anticorrosive coating.
The anticorrosive coatings of examples 1-3 and comparative examples 1-6 were tested for their performance, as shown in table 1:
wherein, adhesion (pull-off adhesion): GB/T5210; the corrosion resistance is tested according to national standards GB/T9274-88 and GB/T1771-91.
Table 1:
as can be seen from the table, the modified graphene water-based anticorrosive coating prepared by the invention has excellent adhesion and anticorrosive performance, and thus has excellent application prospects.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The modified graphene water-based anticorrosive paint is characterized in that: the anticorrosive paint comprises the following raw materials in parts by weight:
55-65 parts of water-based epoxy resin; 4-8 parts of octadecylamine and silane co-modified graphene oxide and 2-4 parts of silane modified zinc-copper-iron hydrotalcite; 15-25 parts of a diluent; 8-16 parts of a curing agent; 3-7 parts of a dispersing agent and 3-5 parts of a defoaming agent; 3-5 parts of a coupling agent.
2. The modified graphene water-based anticorrosive paint according to claim 1, characterized in that: the preparation method of the octadecylamine and silane coupling agent co-modified graphene oxide comprises the following steps:
adding graphene oxide into an ethanol solution containing octadecylamine and a silane coupling agent for reaction, and then centrifuging, washing and drying to obtain the octadecylamine and silane co-modified graphene oxide.
3. The modified graphene water-based anticorrosive paint as claimed in claim 2, wherein: the silane coupling agent is at least one of KH550, KH560 and KH 570.
4. The modified graphene water-based anticorrosive paint according to claim 2, characterized in that: the mass ratio of the graphene oxide to the octadecylamine to the silane coupling agent is 1.2-0.4: 0.1 to 0.3; the reaction is carried out at the temperature of 60-80 ℃ for 12-18 h; the drying is carried out for 10 to 18 hours at the temperature of between 80 and 120 ℃.
5. The modified graphene water-based anticorrosive paint according to claim 1, characterized in that: the preparation method of the silane modified zinc-copper-iron hydrotalcite comprises the following steps: (a) Weighing copper salt, zinc salt and iron salt, dissolving the copper salt, the zinc salt and the iron salt in deionized water to prepare a mixed salt solution, stirring, then dropwise adding alkali liquor to adjust the pH of the solution, then transferring the solution to a hydrothermal reaction kettle for reaction, centrifuging, washing, drying and grinding to obtain zinc-copper-iron hydrotalcite; (b) And (b) adding the zinc-copper-iron hydrotalcite obtained in the step (a) into a silane coupling agent ethanol solution for reaction, and then centrifuging, washing and drying to obtain the silane modified zinc-copper-iron hydrotalcite.
6. The modified graphene water-based anticorrosive paint according to claim 5, characterized in that: in step (a); the stirring time is 20-40 min, and the pH value is 9-11; the hydrothermal reaction is carried out for 10 to 16 hours at a temperature of between 120 and 140 ℃; the drying is carried out for 14 to 20 hours at a temperature of between 80 and 120 ℃.
7. The modified graphene water-based anticorrosive paint as claimed in claim 5, wherein: in step (b); the concentration of the ethanol solution of the silane coupling agent is 2-4 mol/L; the reaction is carried out for 5 to 9 hours at a temperature of between 60 and 80 ℃; the drying is carried out for 14 to 20 hours at a temperature of between 80 and 100 ℃.
8. The modified graphene water-based anticorrosive paint as claimed in claim 5, wherein: the copper salt is at least one of copper acetate, copper chloride and copper nitrate; the zinc salt is at least one of zinc nitrate, zinc acetate and zinc chloride; the ferric salt is at least one of ferric nitrate, ferric chloride and ferric acetate; the alkali is sodium carbonate and sodium hydroxide; the molar ratio of the sodium carbonate to the sodium hydroxide is 1:0.2 to 0.4; in the step (a), the molar ratio of copper, zinc and iron is 1:1:2-4: the concentration of the alkali liquor is 2-4 mol/L, and in the step (b), the molar ratio of the copper to the silane is 1; the silane is at least one of KH550, KH560 and KH 570.
9. The modified graphene water-based anticorrosive paint according to claim 1, characterized in that: the diluent is water; the curing agent is at least one of waterborne epoxy curing agent EA-15, waterborne epoxy curing agent EA-31 and waterborne epoxy curing agent H202B; the dispersant is at least one of BYK-180, BYK-190 and BYK-192; the defoaming agent is at least one of BYK-019, BYK-024 and BYK-028; the coupling agent is at least one of KH550, KH560 and KH 570.
10. The preparation method of the modified graphene water-based anticorrosive paint according to any one of claims 1 to 9, characterized in that: the preparation method comprises the following steps of firstly putting the waterborne epoxy resin, octadecylamine and silane co-modified graphene oxide, silane modified zinc-copper-iron hydrotalcite and a diluent into a high-speed stirrer to be mixed, stirring at the speed of 3000-4000 r/min for 20-60 min, then adding the curing agent, the dispersing agent, the defoaming agent and the coupling agent into the mixture, and continuously stirring for 20-40 min to obtain the anticorrosive coating.
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