CN111574918A - Preparation method of sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint - Google Patents
Preparation method of sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint Download PDFInfo
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- 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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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/635—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto unsaturated polymers
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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
Abstract
The invention discloses a preparation method of a sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint, which comprises the steps of firstly preparing graphene oxide, then sulfonating to obtain sulfonic acid type graphene, and then preparing an acrylic acid modified epoxy resin intermediate from bisphenol A type epoxy resin and acrylic acid; 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 a polyurethane-epoxy resin core-shell emulsion; and finally, mixing the polyurethane-epoxy resin core-shell emulsion with the sulfonic acid type graphene to obtain the anticorrosive paint. The invention greatly improves the corrosion resistance of the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint, and the corrosion potential of the coating is increased and the corrosion current density is reduced along with the increase of the content of the sulfonic acid type graphene, so that the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint 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 sulfonic acid type graphene/polyurethane-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 sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint, 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 sulfonic acid type graphene/polyurethane-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;
dissolving graphene oxide in deionized water, adding sodium aminopolyether sulfonate into a solution of the graphene oxide, adjusting the pH of the system to 9-10 by using sodium hydroxide, stirring and heating for reaction, reducing the temperature of the system to room temperature after the reaction is finished, filtering, washing the system to be neutral by using the deionized water, adding sodium borohydride and ammonia water, heating, stirring for reaction, filtering after the reaction is finished, and performing vacuum drying on a filter to obtain sulfonic acid type graphene;
step three, 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 four, putting hydroxyethyl methacrylate, the 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 hydroxyl acrylic resin, xylene and hexamethylene diisocyanate into a stainless steel container, then adding an emulsifier aqueous solution dissolved with OP-10, and putting the emulsifier aqueous solution into a high-speed dispersion machine for dispersion and stirring to obtain a shell-phase monomer pre-emulsion;
step five, 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 six, slowly dripping the shell-phase monomer pre-emulsion prepared in the step four 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 polyurethane-epoxy resin core-shell emulsion;
and step seven, putting the polyurethane-epoxy resin core-shell emulsion prepared in the step six into a dispersion machine, slowly adding the sulfonic acid type graphene prepared in the step two, and stirring for 1 hour to obtain the sulfonic acid type graphene/polyurethane-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, 500-550 mg of sodium amino polyether sulfonate, 0.5-0.6 g of sodium borohydride and 1-2 mL of ammonia water are added into each 100mL of graphene oxide solution; wherein the concentration of the graphene oxide solution is 5 mg/mL.
In the third step, the reaction molar ratio of the bisphenol A epoxy resin to the acrylic acid is 1: 1.
In the fourth step, the mass ratio of the hydroxyl acrylic resin, the dimethylbenzene and the hexamethylene diisocyanate is 6:20: 1.
In the fourth 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 fourth 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 fifth 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 seventh step, 10-15 g of sulfonic acid type graphene is added to every 100g of polyurethane-epoxy resin core-shell emulsion.
The invention has the beneficial effects that:
according to the invention, sulfonic acid type graphene is dispersed into polyurethane-epoxy resin core-shell emulsion, and the amino polyether sodium sulfonate is grafted to the graphene oxide by taking an epoxy group on the surface of the graphene oxide as a reaction active point and combining nucleophilic ring opening, so that the corrosion resistance of the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint is greatly improved. With the increase of the sulfonic acid type graphene/content, 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.
1. A preparation method of a sulfonic acid type graphene/polyurethane-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;
dissolving graphene oxide in deionized water, adding sodium aminopolyether sulfonate into a solution of the graphene oxide, adjusting the pH of the system to 9-10 by using sodium hydroxide, stirring and heating for reaction, reducing the temperature of the system to room temperature after the reaction is finished, filtering, washing the system to be neutral by using the deionized water, adding sodium borohydride and ammonia water, heating, stirring for reaction, filtering after the reaction is finished, and performing vacuum drying on a filter to obtain sulfonic acid type graphene;
step three, 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 four, putting hydroxyethyl methacrylate, the 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 hydroxyl acrylic resin, xylene and hexamethylene diisocyanate into a stainless steel container, then adding an emulsifier aqueous solution dissolved with OP-10, and putting the emulsifier aqueous solution into a high-speed dispersion machine for dispersion and stirring to obtain a shell-phase monomer pre-emulsion;
step five, 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 six, slowly dripping the shell-phase monomer pre-emulsion prepared in the step four 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 polyurethane-epoxy resin core-shell emulsion;
and step seven, putting the polyurethane-epoxy resin core-shell emulsion prepared in the step six into a dispersion machine, slowly adding the sulfonic acid type graphene prepared in the step two, and stirring for 1 hour to obtain the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint.
Example 1
A preparation method of a sulfonic acid type graphene/polyurethane-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;
dissolving graphene oxide in deionized water, taking 100mL of graphene oxide solution with the concentration of 5mg/mL, adding 500mg of sodium aminopolyether sulfonate into the graphene oxide solution, adjusting the pH of the system to 9 by using 10% of sodium hydroxide, stirring and heating to 80 ℃ for reaction for 24 hours, reducing the temperature of the system to 25 ℃ after the reaction is finished, filtering, washing with deionized water to be neutral, adding 0.5g of sodium borohydride and 1mL of ammonia water, heating to 90 ℃, stirring and reacting for 3 hours, filtering after the reaction is finished, and performing vacuum drying on the filtrate at the temperature of 50 ℃ for 7 hours to obtain sulfonic acid type graphene;
step three, 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 four, taking 35g of hydroxyethyl methacrylate, 45g of the acrylic acid modified epoxy resin intermediate, 35g of methyl methacrylate and 10g of butyl acrylate in a stainless steel container, then adding 30g of the emulsifier aqueous solution in which OP-10 is dissolved, placing the emulsifier aqueous solution in a high-speed dispersion machine, and stirring the emulsifier aqueous solution for 30min at the rotating speed of 3000r/min to obtain a nuclear phase monomer pre-emulsion; putting 6g of hydroxyl acrylic resin, 20g of dimethylbenzene and 1g of hexamethylene diisocyanate in a stainless steel container, then adding 20g of emulsifier aqueous solution in which OP-10 is dissolved, and putting the mixture in a high-speed dispersion machine to stir for 30min at the rotating speed of 3000r/min to obtain a shell-phase monomer pre-emulsion;
step five, adding deionized water and OP-10 into a reaction container, heating to 80 ℃, 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 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 six, slowly dripping the shell-phase monomer pre-emulsion prepared in the step four 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 polyurethane-epoxy resin core-shell emulsion;
and step seven, taking 100g of the polyurethane-epoxy resin core-shell emulsion prepared in the step six, dispersing in a dispersion machine at the speed of 1000r/min, then slowly adding 10g of the sulfonic acid type graphene prepared in the step two, and stirring for 1 hour to obtain the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint.
Example 2
A preparation method of a sulfonic acid type graphene/polyurethane-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;
dissolving graphene oxide in deionized water, taking 100mL of graphene oxide solution with the concentration of 5mg/mL, adding 550mg of sodium aminopolyether sulfonate into the graphene oxide solution, adjusting the pH of the system to 9 by using 10% of sodium hydroxide, stirring and heating to 80 ℃ for reaction for 24 hours, reducing the temperature of the system to 25 ℃ after the reaction is finished, filtering, washing with deionized water to be neutral, adding 0.6g of sodium borohydride and 1.5mL of ammonia water, heating to 90 ℃, stirring and reacting for 3 hours, filtering after the reaction is finished, and performing vacuum drying on the filtrate at the temperature of 50 ℃ for 7 hours to obtain sulfonic acid type graphene;
step three, 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 four, 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; putting 6g of hydroxyl acrylic resin, 20g of dimethylbenzene and 1g of hexamethylene diisocyanate in a stainless steel container, then adding 20g of emulsifier aqueous solution in which OP-10 is dissolved, and putting the mixture in a high-speed dispersion machine to stir for 30min at the rotating speed of 3000r/min to obtain a shell-phase monomer pre-emulsion;
step five, adding deionized water and OP-10 into a reaction container, heating to 80 ℃, 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 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 six, slowly dripping the shell-phase monomer pre-emulsion prepared in the step four 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 polyurethane-epoxy resin core-shell emulsion;
and step seven, taking 100g of the polyurethane-epoxy resin core-shell emulsion prepared in the step six, dispersing in a dispersion machine at the speed of 1000r/min, then slowly adding 15g of the sulfonic acid type graphene prepared in the step two, and stirring for 1 hour to obtain the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint.
Example 3
A preparation method of a sulfonic acid type graphene/polyurethane-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;
dissolving graphene oxide in deionized water, taking 100mL of graphene oxide solution with the concentration of 5mg/mL, adding 500mg of sodium aminopolyether sulfonate into the graphene oxide solution, adjusting the pH of the system to 9 by using 10% of sodium hydroxide, stirring and heating to 80 ℃ for reaction for 24 hours, reducing the temperature of the system to 25 ℃ after the reaction is finished, filtering, washing with deionized water to be neutral, adding 0.6g of sodium borohydride and 2mL of ammonia water, heating to 90 ℃, stirring and reacting for 3 hours, filtering after the reaction is finished, and performing vacuum drying on the filtrate at the temperature of 50 ℃ for 7 hours to obtain sulfonic acid type graphene;
step three, 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 four, 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 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; putting 6g of hydroxyl acrylic resin, 20g of dimethylbenzene and 1g of hexamethylene diisocyanate in a stainless steel container, then adding 20g of emulsifier aqueous solution in which OP-10 is dissolved, and putting the mixture in a high-speed dispersion machine to stir for 30min at the rotating speed of 3000r/min to obtain a shell-phase monomer pre-emulsion;
step five, adding deionized water and OP-10 into a reaction container, heating to 80 ℃, 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 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 six, slowly dripping the shell-phase monomer pre-emulsion prepared in the step four 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 polyurethane-epoxy resin core-shell emulsion;
and step seven, taking 100g of the polyurethane-epoxy resin core-shell emulsion prepared in the step six, dispersing in a dispersion machine at the speed of 1000r/min, then slowly adding 12g of the sulfonic acid type graphene prepared in the step two, and stirring for 1 hour to obtain the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint.
Comparative example 1
Comparative example 1 only a polyurethane-epoxy core-shell emulsion was prepared as in example 1, wherein no graphene or modified graphene was added.
Examples of the experiments
Weighing 80g of sulfonic acid type graphene/polyurethane-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
As can be seen from table 1 above, the sulfonic acid type graphene components are contained in examples 1, 2 and 3, and the flexibility, pencil hardness and adhesion of the coating are increased, because the epoxy groups on the surface of the graphene oxide serve as reactive sites, the activity of the reactive sites is improved by ring opening of the epoxy groups, and the sulfonic acid type graphene 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 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 layer without the sulfonic acid type graphene 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 layer.
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 (10)
1. A preparation method of a sulfonic acid type graphene/polyurethane-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;
dissolving graphene oxide in deionized water, adding sodium aminopolyether sulfonate into a solution of the graphene oxide, adjusting the pH of the system to 9-10 by using sodium hydroxide, stirring and heating for reaction, reducing the temperature of the system to room temperature after the reaction is finished, filtering, washing the system to be neutral by using the deionized water, adding sodium borohydride and ammonia water, heating, stirring for reaction, filtering after the reaction is finished, and performing vacuum drying on a filter to obtain sulfonic acid type graphene;
step three, 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 four, putting hydroxyethyl methacrylate, the 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 hydroxyl acrylic resin, xylene and hexamethylene diisocyanate into a stainless steel container, then adding an emulsifier aqueous solution dissolved with OP-10, and putting the emulsifier aqueous solution into a high-speed dispersion machine for dispersion and stirring to obtain a shell-phase monomer pre-emulsion;
step five, 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 six, slowly dripping the shell-phase monomer pre-emulsion prepared in the step four 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 polyurethane-epoxy resin core-shell emulsion;
and step seven, putting the polyurethane-epoxy resin core-shell emulsion prepared in the step six into a dispersion machine, slowly adding the sulfonic acid type graphene prepared in the step two, and stirring for 1 hour to obtain the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint.
2. The preparation method of the sulfonic acid type graphene/polyurethane-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 sulfonic acid type graphene/polyurethane-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, 500-550 mg of sodium amino polyether sulfonate, 0.5-0.6 g of sodium borohydride and 1-2 mL of ammonia water are added into each 100mL of graphene oxide solution; wherein the concentration of the graphene oxide solution is 5 mg/mL.
5. The preparation method of the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the third step, the reaction molar ratio of the bisphenol A type epoxy resin to the acrylic acid is 1: 1.
6. The preparation method of the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the fourth step, the mass ratio of the hydroxyl acrylic resin, the dimethylbenzene and the hexamethylene diisocyanate is 6:20: 1.
7. The preparation method of the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the fourth 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.
8. The preparation method of the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the fourth 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.
9. The preparation method of the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: in the fifth 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.
10. The preparation method of the sulfonic acid type graphene/polyurethane-epoxy resin composite anticorrosive paint according to claim 1, characterized in that: and seventhly, adding 10-15 g of sulfonic acid type graphene into every 100g of polyurethane-epoxy resin core-shell emulsion.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186808A (en) * | 2007-12-14 | 2008-05-28 | 华南理工大学 | Method for preparing graphite series nano fluid |
| CN106632878A (en) * | 2016-12-15 | 2017-05-10 | 陕西科技大学 | Oxidized graphene/waterborne polyurethane acrylate composite emulsion and preparation method and application thereof |
| CN109852181A (en) * | 2018-12-29 | 2019-06-07 | 江西原石科技有限公司 | The preparation method of epoxy modified acrylic resin antirust emulsion |
-
2020
- 2020-06-11 CN CN202010528834.5A patent/CN111574918A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186808A (en) * | 2007-12-14 | 2008-05-28 | 华南理工大学 | Method for preparing graphite series nano fluid |
| CN106632878A (en) * | 2016-12-15 | 2017-05-10 | 陕西科技大学 | Oxidized graphene/waterborne polyurethane acrylate composite emulsion and preparation method and application thereof |
| CN109852181A (en) * | 2018-12-29 | 2019-06-07 | 江西原石科技有限公司 | The preparation method of epoxy modified acrylic resin antirust emulsion |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113736344A (en) * | 2021-09-26 | 2021-12-03 | 鞠慧 | Water-based epoxy anticorrosive paint and preparation method thereof |
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