CN111518450A - Preparation method of graphene oxide/acrylate-epoxy resin composite anticorrosive paint - Google Patents
Preparation method of graphene oxide/acrylate-epoxy resin composite anticorrosive paint Download PDFInfo
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- CN111518450A CN111518450A CN202010529455.8A CN202010529455A CN111518450A CN 111518450 A CN111518450 A CN 111518450A CN 202010529455 A CN202010529455 A CN 202010529455A CN 111518450 A CN111518450 A CN 111518450A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
The invention discloses a preparation method of graphene oxide/acrylate-epoxy resin composite anticorrosive paint, which comprises the steps of firstly preparing graphene oxide, and then preparing an acrylic acid modified epoxy resin intermediate from bisphenol A epoxy resin and acrylic acid; then, respectively preparing a core-phase monomer pre-emulsion and a shell-phase monomer pre-emulsion, and carrying out core-shell reaction polymerization on the core-phase monomer pre-emulsion and the shell-phase monomer pre-emulsion through an initiator to obtain an acrylate-epoxy resin core-shell emulsion; and finally, mixing the acrylate-epoxy resin core-shell emulsion with graphene oxide to obtain the anticorrosive coating. According to the invention, the epoxy group on the surface of the graphene oxide is used as a reaction active point, so that the corrosion resistance of the graphene oxide/acrylate-epoxy resin composite anticorrosive coating is greatly improved. With the increase of the content of the graphene oxide, the corrosion potential of the coating is increased, and the corrosion current density is reduced, so that the coating has excellent metal corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of organic anticorrosive coatings, and particularly relates to a preparation method of a graphene oxide/acrylate-epoxy resin composite anticorrosive coating.
Background
The anticorrosive paint coating is a film layer which is formed by coating a liquid mixture on the surface of a material in a mode of air spraying, dip coating, brush coating and the like and has corrosion resistance and can block corrosive media after being cured. The coating has low curing temperature, simple operation and construction, low cost and good corrosion prevention effect, and is an ideal metal surface corrosion prevention mode. At present, the surface anticorrosive coatings of metal materials are various in types and are divided into organic protective coatings and inorganic protective coatings. The inorganic anticorrosive paint is prepared with silicate or phosphate compound as adhesive and through adding pigment, assistant, curing agent, etc. Compared with inorganic protective coatings, the organic protective coatings mainly comprise polyurethane coatings, epoxy resin coatings, vinyl chloride-containing coatings and the like, and the resins are widely applied to metal anticorrosive coatings due to the characteristics of medium resistance, high hardness, excellent thermal stability, excellent chemical stability and the like. With the improvement of environmental protection awareness and environmental requirements, an environmental-friendly coating becomes the development focus of the industry. Particularly, the composite system prepared from the epoxy resin emulsion modified by polyurethane or acrylic ester not only has the high modulus, high strength and excellent corrosion resistance of the epoxy resin, but also has the properties of composite components, such as high glossiness, weather resistance, high wear resistance and the like.
Due to the unique structure of the graphene material, the graphene material has a plurality of excellent physicochemical properties including outstanding heat conduction and electric conductivity, thermal stability and chemical stability, higher flexibility and the like, is a preferable reinforcing agent for composite materials, and is particularly suitable for the field of protection of metal surface corrosion and oxidation. However, the graphene is mainly deposited and transferred by CVD, EPD and the like, and the chemical deposition and thin film transfer methods have high requirements on equipment and very complex processes, which also limits the development of graphene in the aqueous anticorrosive coating.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene oxide/acrylate-epoxy resin composite anticorrosive coating, aiming at the problems in the prior art.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a preparation method of a graphene oxide/acrylate-epoxy resin composite anticorrosive paint comprises the following steps:
placing graphene and sodium nitrate into a reaction container in an ice-water bath at 0 ℃, adding concentrated sulfuric acid, stirring until the mixture is uniformly mixed, then gradually adding potassium permanganate, transferring the reaction container into a constant-temperature water bath after the dropwise addition is finished, slowly dropwise adding deionized water for reaction, adding aqueous hydrogen peroxide after the reaction is finished until the reaction solution becomes bright yellow, then placing the reaction container into a centrifuge tube, centrifuging until the pH of the supernatant is neutral, removing the colloid on the lower layer, and performing vacuum drying to obtain graphene oxide;
step two, putting bisphenol A type epoxy resin and tetrabutylammonium bromide into a reaction container, then dropwise adding acrylic acid into the reaction container, completing dropwise adding within 1 hour, and continuing to perform heat preservation reaction to obtain an acrylic acid modified epoxy resin intermediate;
step three, putting hydroxyethyl methacrylate, an acrylic acid modified epoxy resin intermediate, methyl methacrylate and butyl acrylate into a stainless steel container, then adding an emulsifier aqueous solution in which OP-10 is dissolved, and putting the emulsifier aqueous solution into a high-speed dispersion machine for dispersion and stirring to obtain a nuclear phase monomer pre-emulsion; putting polyethylene glycol acrylate, methyl methacrylate, butyl acrylate and vinyl triisopropoxysilane into a stainless steel container, adding an emulsifier aqueous solution with OP-10 dissolved therein, and placing the emulsifier aqueous solution into a high-speed dispersion machine for dispersion and stirring to obtain a shell phase monomer pre-emulsion;
step four, adding deionized water and OP-10 into a reaction container, heating and stirring until emulsion is completely dissolved, then adding one fifth of the nuclear phase monomer pre-emulsion prepared in the step three into the reaction container, slowly dripping one fourth of initiator aqueous solution for reaction, after reacting for a period of time, dripping the rest nuclear phase monomer pre-emulsion and the initiator aqueous solution into the reaction container at constant speed to obtain nuclear phase emulsion;
step five, slowly dripping the shell-phase monomer pre-emulsion prepared in the step three into the core-phase emulsion, continuing to perform heat preservation reaction after finishing dripping, then cooling to remove residual monomers, adding ammonia water to adjust the pH value to 7-8, and filtering to obtain the acrylate-epoxy resin core-shell emulsion;
and step six, putting the acrylate-epoxy resin core-shell emulsion prepared in the step five into a dispersion machine, slowly adding the graphene oxide prepared in the step one, and stirring for 1 hour to obtain the graphene oxide/acrylate-epoxy resin composite anticorrosive paint.
In order to optimize the above technical solution, the specific measures taken further include:
in the first step, the mass ratio of the graphene to the sodium nitrate to the potassium permanganate is 2:1: 6.
In the first step, the dripping speed of the potassium permanganate is 0.06-0.07 g/min.
In the second step, the reaction molar ratio of the bisphenol A epoxy resin to the acrylic acid is 1: 1.
In the third step, the mass ratio of the hydroxyethyl methacrylate to the acrylic acid modified epoxy resin intermediate to the methyl methacrylate to the butyl acrylate is (2-5): (3-6): (2-5): 1.
In the third step, the mass ratio of the polyethylene glycol acrylate, the methyl methacrylate, the butyl acrylate and the vinyl triisopropoxysilane is (1-3): 2-5): 1: (0.6-0.8).
In the third step, the dispersing in the high-speed disperser is specifically that stirring is carried out for 30min at the rotating speed of 3000 r/min.
In the fourth step, the initiator aqueous solution is specifically prepared by: 0.25g of ammonium persulfate and 0.35g of sodium bicarbonate were added per 30g of deionized water.
In the sixth step, 10-15 g of graphene oxide is added to every 100g of the acrylate-epoxy resin core-shell emulsion.
The invention has the beneficial effects that:
according to the invention, graphene oxide is dispersed into the acrylate-epoxy resin core-shell emulsion, and the epoxy group on the surface of the graphene oxide is used as a reaction active point, so that the corrosion resistance of the graphene oxide/acrylate-epoxy resin composite anticorrosive paint is greatly improved. With the increase of the content of the graphene oxide, the corrosion potential of the coating is increased, and the corrosion current density is reduced, so that the coating shows excellent metal corrosion resistance.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a graphene oxide/acrylate-epoxy resin composite anticorrosive paint comprises the following steps:
step one, placing 40g of graphene and 20g of sodium nitrate into a 500mL three-neck flask in an ice-water bath at 0 ℃, adding 80mL of concentrated sulfuric acid, stirring for 30min until the mixture is uniformly mixed, then gradually adding 120g of potassium permanganate, dropwise adding for 90min, transferring a reaction container into a constant-temperature water bath at 40 ℃ after the dropwise adding is finished, slowly dropwise adding 90mL of deionized water for reaction for 1 hour, adding 6mL of a 30% hydrogen peroxide aqueous solution by mass fraction after the reaction is finished until the reaction solution becomes bright yellow, then placing the reaction solution into a centrifuge tube, centrifuging at a speed of 5000r/min until the pH of a supernatant is neutral, taking out a lower-layer colloid, and drying in a vacuum drying oven at 35 ℃ for 72 hours to obtain graphene oxide;
step two, putting bisphenol A epoxy resin and tetrabutylammonium bromide into a reaction vessel, and then dropwise adding a mixture of bisphenol A epoxy resin and bisphenol A epoxy resin in a reaction molar ratio of 1:1, dripping the acrylic acid within 1 hour, and continuing to perform heat preservation reaction for 3 hours to obtain an acrylic acid modified epoxy resin intermediate;
step three, taking 35g of hydroxyethyl methacrylate, 45g of acrylic acid modified epoxy resin intermediate, 35g of methyl methacrylate and 10g of butyl acrylate in a stainless steel container, then adding 30g of emulsifier aqueous solution in which OP-10 is dissolved, placing the mixture in a high-speed dispersion machine, and stirring for 30min at the rotating speed of 3000r/min to obtain nuclear phase monomer pre-emulsion; taking 20g of polyethylene glycol acrylate, 35g of methyl methacrylate, 10g of butyl acrylate and 6g of vinyl triisopropoxysilane in a stainless steel container, then adding 20g of emulsifier aqueous solution dissolved with OP-10, placing the mixture in a high-speed dispersion machine, and stirring the mixture for 30min at a rotating speed of 3000r/min to obtain a shell phase monomer pre-emulsion;
adding deionized water and OP-10 into a reaction container, heating to 80 ℃, stirring until emulsion is completely dissolved, adding one fifth of the nuclear phase monomer pre-emulsion prepared in the step three into the reaction container, slowly dropwise adding one fourth of initiator aqueous solution for reacting for 10min, after reacting for a period of time, dropwise adding the rest nuclear phase monomer pre-emulsion and initiator aqueous solution into the reaction container at constant speed, dropwise adding for 3 hours at constant speed, and after dropwise adding, keeping the temperature for reacting for 30min to obtain nuclear phase emulsion;
step five, slowly dripping the shell-phase monomer pre-emulsion prepared in the step three into the core-phase emulsion, dripping at a constant speed for 3 hours, continuing to perform heat preservation reaction after finishing dripping, then cooling to 50 ℃, adding tert-butyl hydroperoxide to remove residual monomers, adding ammonia water to adjust the pH value to 7, and filtering to obtain the acrylate-epoxy resin core-shell emulsion;
and step six, taking 100g of the acrylate-epoxy resin core-shell emulsion prepared in the step five, dispersing in a dispersion machine at the speed of 1000r/min, then slowly adding 10g of graphene oxide prepared in the step one, and stirring for 1 hour to obtain the graphene oxide/acrylate-epoxy resin composite anticorrosive paint.
Example 2
A preparation method of a graphene oxide/acrylate-epoxy resin composite anticorrosive paint comprises the following steps:
step one, taking 60g of graphene and 30g of sodium nitrate, placing the graphene and the sodium nitrate into a 500mL three-neck flask in an ice-water bath at 0 ℃, adding 80mL of concentrated sulfuric acid, stirring for 30min until the mixture is uniformly mixed, then gradually adding 180g of potassium permanganate, dropwise adding for 90min, transferring a reaction container into a constant-temperature water bath at 40 ℃ after the dropwise adding is finished, slowly dropwise adding 90mL of deionized water for reaction for 1 hour, adding 6mL of a 30% hydrogen peroxide aqueous solution by mass fraction after the reaction is finished until the reaction solution becomes bright yellow, placing the reaction solution into a centrifuge tube, centrifuging at the speed of 5000r/min until the pH of a supernatant is neutral, taking out a lower-layer colloid, and drying in a vacuum drying oven at 35 ℃ for 72 hours to obtain graphene oxide;
step two, putting bisphenol A epoxy resin and tetrabutylammonium bromide into a reaction vessel, and then dropwise adding a mixture of bisphenol A epoxy resin and bisphenol A epoxy resin in a reaction molar ratio of 1:1, dripping the acrylic acid within 1 hour, and continuing to perform heat preservation reaction for 3 hours to obtain an acrylic acid modified epoxy resin intermediate;
step three, taking 40g of hydroxyethyl methacrylate, 30g of acrylic acid modified epoxy resin intermediate, 40g of methyl methacrylate and 12g of butyl acrylate in a stainless steel container, then adding 30g of emulsifier aqueous solution in which OP-10 is dissolved, placing the mixture in a high-speed dispersion machine, and stirring for 30min at the rotating speed of 3000r/min to obtain nuclear phase monomer pre-emulsion; taking 30g of polyethylene glycol acrylate, 40g of methyl methacrylate, 12g of butyl acrylate and 7g of vinyl triisopropoxysilane in a stainless steel container, then adding 20g of emulsifier aqueous solution dissolved with OP-10, placing the mixture in a high-speed dispersion machine, and stirring the mixture for 30min at a rotating speed of 3000r/min to obtain a shell phase monomer pre-emulsion;
adding deionized water and OP-10 into a reaction container, heating to 80 ℃, stirring until emulsion is completely dissolved, adding one fifth of the nuclear phase monomer pre-emulsion prepared in the step three into the reaction container, slowly dropwise adding one fourth of initiator aqueous solution for reacting for 10min, after reacting for a period of time, dropwise adding the rest nuclear phase monomer pre-emulsion and initiator aqueous solution into the reaction container at constant speed, dropwise adding for 3 hours at constant speed, and after dropwise adding, keeping the temperature for reacting for 30min to obtain nuclear phase emulsion;
step five, slowly dripping the shell-phase monomer pre-emulsion prepared in the step three into the core-phase emulsion, dripping at a constant speed for 3 hours, continuing to perform heat preservation reaction after finishing dripping, then cooling to 50 ℃, adding tert-butyl hydroperoxide to remove residual monomers, adding ammonia water to adjust the pH value to 8, and filtering to obtain the acrylate-epoxy resin core-shell emulsion;
and step six, taking 100g of the acrylate-epoxy resin core-shell emulsion prepared in the step five, dispersing in a dispersion machine at the speed of 1000r/min, then slowly adding 15g of graphene oxide prepared in the step one, and stirring for 1 hour to obtain the graphene oxide/acrylate-epoxy resin composite anticorrosive paint.
Example 3
A preparation method of a graphene oxide/acrylate-epoxy resin composite anticorrosive paint comprises the following steps:
step one, placing 20g of graphene and 10g of sodium nitrate into a 500mL three-neck flask in an ice-water bath at 0 ℃, adding 80mL of concentrated sulfuric acid, stirring for 30min until the mixture is uniformly mixed, then gradually adding 60g of potassium permanganate, dropwise adding for 90min, transferring a reaction container into a constant-temperature water bath at 40 ℃ after the dropwise adding is finished, slowly dropwise adding 90mL of deionized water for reaction for 1 hour, adding 6mL of a 30% hydrogen peroxide aqueous solution by mass fraction after the reaction is finished until the reaction solution becomes bright yellow, then placing the reaction solution into a centrifuge tube, centrifuging at a speed of 5000r/min until the pH of a supernatant is neutral, taking out a lower-layer colloid, and drying in a vacuum drying oven at 35 ℃ for 72 hours to obtain graphene oxide;
step two, putting bisphenol A epoxy resin and tetrabutylammonium bromide into a reaction vessel, and then dropwise adding a mixture of bisphenol A epoxy resin and bisphenol A epoxy resin in a reaction molar ratio of 1:1, dripping the acrylic acid within 1 hour, and continuing to perform heat preservation reaction for 3 hours to obtain an acrylic acid modified epoxy resin intermediate;
step three, taking 10g of hydroxyethyl methacrylate, 50g of acrylic acid modified epoxy resin intermediate, 20g of methyl methacrylate and 8g of butyl acrylate in a stainless steel container, then adding an emulsifier aqueous solution 30 in which OP-10 is dissolved, placing the emulsifier aqueous solution in a high-speed dispersion machine, and stirring for 30min at the rotating speed of 3000r/min to obtain a nuclear phase monomer pre-emulsion; taking 10g of polyethylene glycol acrylate, 20g of methyl methacrylate, 10g of butyl acrylate and 8g of vinyl triisopropoxysilane in a stainless steel container, then adding 20g of emulsifier aqueous solution dissolved with OP-10, placing the mixture in a high-speed dispersion machine, and stirring the mixture for 30min at a rotating speed of 3000r/min to obtain a shell phase monomer pre-emulsion;
adding deionized water and OP-10 into a reaction container, heating to 80 ℃, stirring until emulsion is completely dissolved, adding one fifth of the nuclear phase monomer pre-emulsion prepared in the step three into the reaction container, slowly dropwise adding one fourth of initiator aqueous solution for reacting for 10min, after reacting for a period of time, dropwise adding the rest nuclear phase monomer pre-emulsion and initiator aqueous solution into the reaction container at constant speed, dropwise adding for 3 hours at constant speed, and after dropwise adding, keeping the temperature for reacting for 30min to obtain nuclear phase emulsion;
step five, slowly dripping the shell-phase monomer pre-emulsion prepared in the step three into the core-phase emulsion, dripping at a constant speed for 3 hours, continuing to perform heat preservation reaction after finishing dripping, then cooling to 50 ℃, adding tert-butyl hydroperoxide to remove residual monomers, adding ammonia water to adjust the pH value to 7, and filtering to obtain the acrylate-epoxy resin core-shell emulsion;
and step six, taking 100g of the acrylate-epoxy resin core-shell emulsion prepared in the step five, dispersing in a dispersion machine at the speed of 1000r/min, then slowly adding 12g of graphene oxide prepared in the step one, and stirring for 1 hour to obtain the graphene oxide/acrylate-epoxy resin composite anticorrosive paint.
Comparative example 1
In comparative example 1, only the acrylate-epoxy core-shell emulsion was prepared, and the preparation method was the same as in example 1.
Examples of the experiments
Weighing 80g of graphene oxide/acrylate-epoxy resin composite anticorrosive paint and 30g of deionized water in a stainless steel container, stirring for 10min at the rotating speed of 1000r/min, then adding an antifoaming agent 156 with the mass fraction of 0.3% of the anticorrosive paint and a leveling agent 452 with the mass fraction of 0.4%, stirring for 15min, slowly adding 2g of diethylene glycol butyl ether and an aqueous amino resin curing agent with the same molar weight as an epoxy group, then adding a thickening agent 69 with the mass fraction of 0.3% of the anticorrosive paint, continuously stirring for 15min until foams are completely eliminated, obtaining the aqueous paint, and sealing for later use.
The metal substrate adopts iron sheets, the iron sheets are processed into the time of 100mm multiplied by 80mm multiplied by 0.5mm, and the iron sheets are pretreated for oil removal and rust removal before coating in order to improve the adhesive force between the substrate and the coating. The coating prepared above was applied to the surface of the metal sheet according to a roll coating method. The prepared coating is tested for flexibility, adhesion, pencil hardness and electrochemical performance, and the specific results are shown in tables 1 and 2 below. The flexibility test refers to GB/T1731-1993 paint film flexibility determination method, the adhesion refers to GB 1720-1979 paint film adhesion determination method, the pencil hardness refers to GB/T6739-2006 paint and varnish pencil method for determining paint film hardness, the electrochemical performance adopts a three-electrode system workstation determination experiment, a saturated calomel electrode and a platinum electrode are respectively adopted as a reference electrode and an auxiliary electrode, a working electrode is a coating, and an electrolyte solution is a 3.5% NaCl solution.
Table 1 physical properties of graphene coatings with different contents
| Flexibility/grade | Adhesion/grade | Hardness of pencil | |
| Example 1 | 4 | 2 | 2H |
| Example 2 | 4 | 2 | 3H |
| Comparative example 3 | 4 | 2 | 2H |
| Comparative example 1 | 10 | 1 | 1H |
As can be seen from table 1 above, the graphene oxide components are contained in examples 1, 2 and 3, and the flexibility, pencil hardness and adhesion of the coating are all increased, because the epoxy groups on the surface of the graphene oxide serve as reactive sites, the epoxy groups are crosslinked and can be uniformly dispersed in the acrylate-epoxy resin emulsion, and the graphene oxide itself has higher hardness and better interlayer lubrication function, compared with comparative example 1, the modified coating has no defects such as cracks and bubbles, and all indexes meet the national standard requirements, and the modified coating has more stable and excellent performance.
TABLE 2 electrochemical Properties of the coatings of the different examples
As can be seen from Table 2, the self-corrosion potential values in examples 1, 2 and 3 are large, and the corresponding self-corrosion current values are small, so that the corrosion resistance of the coating is the highest. The results of comparative example 1 show that the self-corrosion potential of the coating without the addition of graphene oxide is reduced, the self-corrosion current value is high, and corrosion of the metal surface occurs, and thus it is known that the addition of graphene oxide in the system further improves the corrosion resistance of the coating.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (9)
1. A preparation method of a graphene oxide/acrylate-epoxy resin composite anticorrosive paint is characterized by comprising the following steps:
placing graphene and sodium nitrate into a reaction container in an ice-water bath at 0 ℃, adding concentrated sulfuric acid, stirring until the mixture is uniformly mixed, then gradually adding potassium permanganate, transferring the reaction container into a constant-temperature water bath after the dropwise addition is finished, slowly dropwise adding deionized water for reaction, adding aqueous hydrogen peroxide after the reaction is finished until the reaction solution becomes bright yellow, then placing the reaction container into a centrifuge tube, centrifuging until the pH of the supernatant is neutral, removing the colloid on the lower layer, and performing vacuum drying to obtain graphene oxide;
step two, putting bisphenol A type epoxy resin and tetrabutylammonium bromide into a reaction container, then dropwise adding acrylic acid into the reaction container, completing dropwise adding within 1 hour, and continuing to perform heat preservation reaction to obtain an acrylic acid modified epoxy resin intermediate;
step three, putting hydroxyethyl methacrylate, an acrylic acid modified epoxy resin intermediate, methyl methacrylate and butyl acrylate into a stainless steel container, then adding an emulsifier aqueous solution in which OP-10 is dissolved, and putting the emulsifier aqueous solution into a high-speed dispersion machine for dispersion and stirring to obtain a nuclear phase monomer pre-emulsion; putting polyethylene glycol acrylate, methyl methacrylate, butyl acrylate and vinyl triisopropoxysilane into a stainless steel container, adding an emulsifier aqueous solution with OP-10 dissolved therein, and placing the emulsifier aqueous solution into a high-speed dispersion machine for dispersion and stirring to obtain a shell phase monomer pre-emulsion;
step four, adding deionized water and OP-10 into a reaction container, heating and stirring until emulsion is completely dissolved, then adding one fifth of the nuclear phase monomer pre-emulsion prepared in the step three into the reaction container, slowly dripping one fourth of initiator aqueous solution for reaction, after reacting for a period of time, dripping the rest nuclear phase monomer pre-emulsion and the initiator aqueous solution into the reaction container at constant speed to obtain nuclear phase emulsion;
step five, slowly dripping the shell-phase monomer pre-emulsion prepared in the step three into the core-phase emulsion, continuing to perform heat preservation reaction after finishing dripping, then cooling to remove residual monomers, adding ammonia water to adjust the pH value to 7-8, and filtering to obtain the acrylate-epoxy resin core-shell emulsion;
and step six, putting the acrylate-epoxy resin core-shell emulsion prepared in the step five into a dispersion machine, slowly adding the graphene oxide prepared in the step one, and stirring for 1 hour to obtain the graphene oxide/acrylate-epoxy resin composite anticorrosive paint.
2. The preparation method of the graphene oxide/acrylate-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the first step, the mass ratio of the graphene to the sodium nitrate to the potassium permanganate is 2:1: 6.
3. The preparation method of the graphene oxide/acrylate-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the first step, the dripping speed of the potassium permanganate is 0.06-0.07 g/min.
4. The preparation method of the graphene oxide/acrylate-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the second step, the reaction molar ratio of the bisphenol A type epoxy resin to the acrylic acid is 1: 1.
5. The preparation method of the graphene oxide/acrylate-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the third step, the mass ratio of the hydroxyethyl methacrylate to the acrylic acid modified epoxy resin intermediate to the methyl methacrylate to the butyl acrylate is (2-5): (3-6): (2-5): 1.
6. The preparation method of the graphene oxide/acrylate-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the third step, the mass ratio of the polyethylene glycol acrylate, the methyl methacrylate, the butyl acrylate and the vinyl triisopropoxysilane is (1-3): 2-5): 1: (0.6-0.8).
7. The preparation method of the graphene oxide/acrylate-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the third step, the dispersing in the high-speed dispersing machine specifically means stirring for 30min at the rotating speed of 3000 r/min.
8. The preparation method of the graphene oxide/acrylate-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the fourth step, the initiator aqueous solution is specifically prepared by: 0.25g of ammonium persulfate and 0.35g of sodium bicarbonate were added per 30g of deionized water.
9. The preparation method of the graphene oxide/acrylate-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the sixth step, 10-15 g of graphene oxide is added into every 100g of acrylate-epoxy resin core-shell emulsion.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680016A (en) * | 2020-12-22 | 2021-04-20 | 余小翠 | Automobile paint component and preparation method thereof |
| CN113337168A (en) * | 2021-05-20 | 2021-09-03 | 惠州深赛尔化工有限公司 | Acrylic resin can water-based paint and preparation method thereof |
| CN113683938A (en) * | 2021-08-23 | 2021-11-23 | 亚士创能科技(上海)股份有限公司 | Epoxy graphene intermediate and preparation method and application thereof |
| CN113698837A (en) * | 2021-08-11 | 2021-11-26 | 浙江省产品质量安全科学研究院 | Preparation method of single-component water-based hybrid electromagnetic shielding coating |
| CN113755077A (en) * | 2021-07-30 | 2021-12-07 | 武汉格林鸿业新材料科技有限公司 | Hydrophobic anti-fouling ultraviolet curing coating and preparation method thereof |
| CN113845822A (en) * | 2021-09-30 | 2021-12-28 | 江阴市玲珑高分子材料有限公司 | Energy-saving curing super-weather-resistant powder coating and production process thereof |
| CN114230723A (en) * | 2021-12-28 | 2022-03-25 | 青岛理工大学 | Graphene oxide modified styrene-acrylic pickering emulsion, composite emulsion, and preparation method and application thereof |
| CN114836101A (en) * | 2022-05-12 | 2022-08-02 | 陈小花 | Graphene composite coating |
| CN115073100A (en) * | 2022-07-12 | 2022-09-20 | 江西省萍乡市华东出口电瓷有限公司 | High-strength durable porcelain insulator cement adhesive and preparation method thereof |
| CN115895325A (en) * | 2022-09-27 | 2023-04-04 | 浩力森化学科技（江苏）有限公司 | Graphene auxiliary agent, main resin, electrophoretic coating emulsion and preparation method thereof |
| CN116042049A (en) * | 2022-12-09 | 2023-05-02 | 江苏云湖新材料科技有限公司 | Graphene modified water-based anticorrosive paint and preparation method thereof |
| CN116948446A (en) * | 2023-06-30 | 2023-10-27 | 河海大学 | Preparation method of nano container loaded with corrosion inhibitor, water-based nano composite anticorrosive paint and preparation method and application thereof |
| CN117866470A (en) * | 2024-03-04 | 2024-04-12 | 成都虹润制漆有限公司 | Modified composite coating for railway bridge steel structure and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112680016A (en) * | 2020-12-22 | 2021-04-20 | 余小翠 | Automobile paint component and preparation method thereof |
| CN113337168A (en) * | 2021-05-20 | 2021-09-03 | 惠州深赛尔化工有限公司 | Acrylic resin can water-based paint and preparation method thereof |
| CN113755077A (en) * | 2021-07-30 | 2021-12-07 | 武汉格林鸿业新材料科技有限公司 | Hydrophobic anti-fouling ultraviolet curing coating and preparation method thereof |
| CN113698837A (en) * | 2021-08-11 | 2021-11-26 | 浙江省产品质量安全科学研究院 | Preparation method of single-component water-based hybrid electromagnetic shielding coating |
| CN113683938A (en) * | 2021-08-23 | 2021-11-23 | 亚士创能科技(上海)股份有限公司 | Epoxy graphene intermediate and preparation method and application thereof |
| CN113845822A (en) * | 2021-09-30 | 2021-12-28 | 江阴市玲珑高分子材料有限公司 | Energy-saving curing super-weather-resistant powder coating and production process thereof |
| CN114230723A (en) * | 2021-12-28 | 2022-03-25 | 青岛理工大学 | Graphene oxide modified styrene-acrylic pickering emulsion, composite emulsion, and preparation method and application thereof |
| CN114836101A (en) * | 2022-05-12 | 2022-08-02 | 陈小花 | Graphene composite coating |
| CN115073100A (en) * | 2022-07-12 | 2022-09-20 | 江西省萍乡市华东出口电瓷有限公司 | High-strength durable porcelain insulator cement adhesive and preparation method thereof |
| CN115895325A (en) * | 2022-09-27 | 2023-04-04 | 浩力森化学科技（江苏）有限公司 | Graphene auxiliary agent, main resin, electrophoretic coating emulsion and preparation method thereof |
| CN115895325B (en) * | 2022-09-27 | 2023-11-14 | 浩力森化学科技（江苏）有限公司 | Graphene auxiliary agent, main resin, electrophoretic coating emulsion and preparation method thereof |
| CN116042049A (en) * | 2022-12-09 | 2023-05-02 | 江苏云湖新材料科技有限公司 | Graphene modified water-based anticorrosive paint and preparation method thereof |
| CN116948446A (en) * | 2023-06-30 | 2023-10-27 | 河海大学 | Preparation method of nano container loaded with corrosion inhibitor, water-based nano composite anticorrosive paint and preparation method and application thereof |
| CN117866470A (en) * | 2024-03-04 | 2024-04-12 | 成都虹润制漆有限公司 | Modified composite coating for railway bridge steel structure and preparation method thereof |
| CN117866470B (en) * | 2024-03-04 | 2024-05-24 | 成都虹润制漆有限公司 | Modified composite coating for railway bridge steel structure and preparation method thereof |
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