CN112980296A - MPA/KH567/rGO reinforced waterborne epoxy amino baking paint and preparation method thereof - Google Patents
MPA/KH567/rGO reinforced waterborne epoxy amino baking paint and preparation method thereof Download PDFInfo
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- 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
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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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Abstract
The invention discloses MPA/KH567/GO reinforced waterborne epoxy amino baking varnish and a preparation method thereof. The method comprises the following steps: GO is prepared by a modified Hummers method, a coupling agent KH567 and 3-mercaptopropionic acid are utilized to modify GO, and silicon hydroxyl is introduced, so that a space is reserved for subsequent performance improvement. The enhancer modified rGO is dispersed in the aqueous epoxy emulsion using a modified phase inversion process without the addition of any surfactants and dispersants. The aqueous epoxy emulsifier is prepared by the reaction of N, N-methylene-bisacrylamide, hydroxyethyl acrylate and epoxy resin E-44. The epoxy equivalent in the waterborne epoxy emulsion and the active hydrogen equivalent in the amino curing agent are uniformly mixed according to the ratio of 1:1 to obtain the MPA/KH567/rGO reinforced waterborne epoxy amino baking paint, which has a certain practical application value.
Description
Technical Field
The invention relates to the field of waterborne epoxy baking varnish, in particular to MPA/KH567/rGO reinforced waterborne epoxy amino baking varnish and a preparation method thereof.
Background
The epoxy resin is a thermosetting resin with excellent performance, has good metal adhesion, corrosion resistance and excellent physical and chemical properties, and is widely applied to the fields of electronics, machinery, buildings, machinery, coatings, advanced composite materials and the like. Epoxy resins of the E-44 type have many advantages, such as excellent chemical resistance; the adhesive force is excellent; the paint film has small shrinkage, high strength and good wear resistance; the epoxy resin has good water resistance, can resist boiling water without falling off, but is only soluble in organic solvents such as aromatic hydrocarbon, ketone and the like and insoluble in water, so the common E-44 type epoxy resin is solvent-based, and the organic solvents have a plurality of defects including toxicity, environmental unfriendliness, flammability, explosiveness and the like, so in recent years, regulations for controlling volatile organic compounds (voc) are successively issued in many regions, and the preparation of the water-based epoxy resin is more and more concerned. However, some groups with good hydrophilicity and strong polarity are introduced into the water-based paint, so that the water resistance and the corrosion resistance of a paint film are reduced, and how to prepare the water-based epoxy baking paint and simultaneously not influence the use effect of the water-based epoxy baking paint as far as possible becomes a research focus in recent years.
Graphene is a new material formed by tightly stacking sp hybridized and connected carbon atoms into a single-layer two-dimensional honeycomb lattice structure, is graphite with a single atomic layer thickness, can be mutually overlapped in a coating through a unique lamellar structure of the graphite, forms a compact isolation layer, and prevents some corrosive media from entering in a physical isolation mode; and the contact angle of the graphene and water is large due to the surface effect of the graphene, the wettability is poor, and water molecules are difficult to absorb by the graphene. After the graphene is added into the water-based epoxy resin, the hydrophobicity of the graphene can prevent water molecules from reaching the surface of the metal matrix through the coating, so that the corrosion is reduced. Because of the excellent properties of graphene, how to uniformly disperse graphene in an aqueous coating is also a hot research in many places.
Disclosure of Invention
At present, a lot of patents exist for applying graphene to epoxy coating, and patents CN110408305A and CN109438761A describe that graphene/reduced graphene is applied to oily epoxy resin, however, in order to disperse graphene into an aqueous epoxy emulsion, a surfactant or a dispersant which is adapted to (better compatible with) graphene, such as polyvinylpyrrolidone (PVP), is usually required to be added, but since one end of a coupling agent KH567 is an epoxy group and the other end is a siloxane group, the hydrophilicity of the coupling agent and the siloxane group is not particularly strong, the coupling agent and the siloxane group are not suitable for dispersing graphene.
An MPA/KH567/rGO reinforced waterborne epoxy amino baking varnish is prepared by using a modified Hummers method to prepare GO, wherein the GO is modified by using KH567 and 3-mercaptopropionic acid. The waterborne epoxy amino baking varnish is prepared by preparing a waterborne epoxy emulsion through a self-made emulsifier, uniformly dispersing rGO into the waterborne epoxy emulsion by using an improved phase inversion method in the preparation process, and then adding a certain proportion of amino resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
an MPA/KH567/rGO reinforced waterborne epoxy amino baking paint comprises the following raw materials in parts by weight:
10-15 parts of water-based epoxy emulsifier
30-50 parts of epoxy resin
35-40 parts of amino resin
0.5-2 parts of reinforcing agent
0.1 to 0.5 portion of defoaming agent
40-70 parts of deionized water
Preferably, the amino resin is EH3870, is purchased from Hengyang Innovation New Polymer materials Co, and has the active hydrogen equivalent of between 400 and 430. The defoaming agent is a BYK organic silicon defoaming agent.
The reinforcing agent MPA/KH567/rGO reinforced waterborne epoxy amino baking varnish comprises the following preparation steps:
(1) GO is prepared by a modified Hummers method:
in an ice-water bath environment, uniformly mixing 2-3 parts of graphite powder and 2-3 parts of sodium nitrate with 30-40 parts of concentrated sulfuric acid and 10-20 parts of concentrated nitric acid, adding 8-10 parts of potassium permanganate for several times, controlling the temperature not to exceed 5 ℃, stirring for a period of time, removing the ice bath, cooling to room temperature, transferring to an electromagnetic water bath kettle, and carrying out electromagnetic stirring for 24 hours. And then slowly adding 100 parts of deionized water, raising the temperature to about 98 ℃, stirring for 20 min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant so that the solution becomes bright yellow. And then centrifugally separating the graphite oxide suspension at the rotating speed of 5000 r/pm, washing the graphite oxide suspension by using deionized water until the separation liquid is neutral, and freeze-drying to obtain GO.
(2) Preparation of enhancer MPA/KH 567/rGO:
dissolving 5-10 parts of GO in deionized water, performing ultrasonic dispersion, adding 0.3-0.5 part of 3-mercaptopropionic acid (MPA) in a 50 ℃ water bath kettle, stirring and reacting for 3-5 hours, and modifying part of GO; heating a water bath to 65 ℃, dissolving 0.4-0.8 part of coupling agent KH567 in 20wt% phosphoric acid solution, adding the solution into GO dispersion, stirring and reacting for 3-6 h, modifying residual GO, centrifugally washing to be neutral, and freeze-drying to obtain an enhancer MPA/KH 567/rGO.
The invention also provides a preparation method of the waterborne epoxy amino baking varnish, which comprises the following steps:
(1) preparing a self-made waterborne epoxy emulsifier:
dissolving 2-5 parts of epoxy resin E-44 in a solvent, adding 0.5-1.5 parts of N, N-methylene bisacrylamide to react with the epoxy resin, adding 0.1 part of potassium persulfate initiator, then slowly dropwise adding 4-8 parts of hydroxyethyl acrylate, heating and stirring to react so that the hydroxyethyl acrylate is subjected to free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, thereby preparing the waterborne epoxy emulsifier.
(2) Preparation of aqueous epoxy emulsion:
weighing 30-50 parts of epoxy resin E-44, adding 0.5-2 parts of reinforcing agent MPA/KH567/rGO, stirring and dispersing uniformly in a 1500r/min dispersion machine, adding 10-15 parts of the aqueous epoxy emulsifier, uniformly mixing in a 2000r/min dispersion machine, slowly dripping 30-50 parts of deionized water within 30min to complete phase inversion, and preparing the aqueous epoxy emulsion.
(3) Preparation of the waterborne epoxy amino baking varnish:
adding 35-40 parts of amino resin and 10-20 parts of deionized water into the waterborne epoxy emulsion, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.1-0.5 part of defoaming agent to finally prepare the waterborne epoxy amino baking paint.
The reinforcing agent is introduced into an aqueous epoxy emulsion system through a process of improving a phase inversion method, and no dispersant or surfactant is added in the process. The improved phase inversion method is characterized in that before the epoxy resin is added with the emulsifier and stirred, the characteristic of good dispersibility of graphene in the epoxy resin is firstly utilized, the epoxy resin and the graphene are uniformly mixed in advance by using a dispersing machine, then the emulsifier is added and mixed with the resin, and deionized water is slowly dripped to complete phase inversion, in the process, the emulsifier coats the mixture of the epoxy resin and the graphene to form latex particles, so that the water-based epoxy emulsion is obtained, and the effect of dispersing the graphene is achieved, wherein the specific flow chart is shown in fig. 4.
The invention has the following remarkable advantages:
1. the water-based baking varnish prepared by the invention has the characteristic of environmental protection, and responds to the national environmental protection policy. The self-made emulsion is a water-based paint, can be removed by washing in the using process, is convenient to use and is easy to store.
2. The water-based epoxy emulsifier used in the invention is a self-made emulsifier, secondary amine in N, N-methylene bisacrylamide is utilized to perform ring-opening reaction with an epoxy group of epoxy resin, double bonds are introduced at the same time, and an initiator potassium persulfate and hydroxyethyl acrylate are added to perform free radical polymerization, so that the epoxy resin-polyhydroxyethyl acrylate type emulsifier is obtained. The emulsifier has a structure similar to that of epoxy resin, so that the emulsifier has good compatibility with the epoxy resin and strong emulsifying capacity, and is a novel water-based epoxy emulsifier.
3. The reinforcing agent prepared in the invention is MPA/KH567/rGO, and the modified graphene is obtained by utilizing 3-mercaptopropionic acid and a coupling agent KH 567. The graphene oxide contains a large amount of polar groups, such as hydroxyl, carboxyl, epoxy and the like, and cannot well prevent corrosive media from entering a substrate when the graphene oxide is applied to a water-based coating, so that the corrosion resistance of the graphene oxide is affected, and therefore the graphene oxide needs to be modified. The modified graphene oxide is obtained by reacting the mercapto group in the 3-mercaptopropionic acid with the epoxy group and reacting the epoxy group in the coupling agent KH567 with the hydroxyl group and the carboxyl group, the content of the polar group on the surface of the modified graphene oxide is reduced, the effect of obstructing corrosive media is improved, and then some defects in a paint film are made up. KH567 also retains some silane groups after modification, leaving room for subsequent modification.
4. The method for dispersing the graphene is an improved phase inversion method, the graphene and the epoxy resin are uniformly dispersed under the high-speed stirring action of a dispersing machine by utilizing the characteristic of excellent compatibility of the graphene and the epoxy resin, and after the epoxy emulsifier is added, the MPA/KH567/rGO reinforced waterborne epoxy baking paint is prepared by gradually dripping deionized water. The graphene has excellent physical properties and barrier properties, and can fill defect holes in a water-based epoxy baking paint coating film, so that the weather resistance, salt spray resistance, pencil hardness, adhesive force and the like of the water-based epoxy baking paint coating film are improved.
Drawings
FIG. 1 SEM picture of the enhancing agent MPA/KH567/rGO used in the present invention; the graph shows that the surface of the prepared modified graphene oxide has more folds, and the modified graphene oxide has stronger hydrophobic capacity because the oxygen-containing functional groups are consumed and reacted in a large amount after modification, so that corrosive media can be prevented from entering more effectively, and the anticorrosion effect is improved.
Figure 2 thisThe Fourier infrared spectrum (FT-IR) of the reinforcing agent MPA/KH567/rGO prepared in the invention; as can be seen from the figure, GO curves at 3495cm-1Shows an absorption peak of hydroxyl at 1740cm-1The absorption peak of carboxyl appears at 910cm-1And 1250cm-1The characteristic absorption peak of the epoxy group is nearby, and the fact that the GO contains a large number of polar groups is proved. After modification, 910cm-1Has a characteristic peak of epoxy substantially disappeared, 2560cm-1A characteristic absorption peak of hydrosulfide group, 1125cm, appears nearby-1The characteristic absorption peak of the silane group appears, which proves that KH567 and 3-mercaptopropionic acid have successfully reacted with GO and modified.
FIG. 3 Fourier transform infrared (FT-IR) spectrum of the aqueous epoxy emulsifier prepared in the present invention; in 1360cm-1The absorption peak of tertiary amine appears near the position, and 910cm-1The characteristic peaks of the adjacent epoxy resin are basically disappeared, and the fact that the methylene bisacrylamide has reacted with the epoxy resin is proved. 1297cm-1The nearby peak represents the appearance of alcoholic hydroxyl group, and 1760cm-1A saturated lactone stretching peak appears nearby, namely that the hydroxyethyl acrylate is connected with the epoxy resin.
FIG. 4 is a flow diagram of the introduction of an enhancer into an aqueous epoxy emulsion system by a modified phase inversion process.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example one
(1) GO is prepared by a modified Hummers method:
a250 ml reaction bottle is assembled in an ice-water bath, 2 parts of graphite powder, 2 parts of sodium nitrate, 30 parts of concentrated sulfuric acid and 15 parts of concentrated nitric acid are uniformly mixed, 8 parts of potassium permanganate is added for several times, the temperature is controlled not to exceed 5 ℃, after stirring for a period of time, the ice bath is removed and the reaction bottle is cooled to room temperature, the reaction bottle is transferred to an electromagnetic water bath kettle, and electromagnetic stirring lasts for 24 hours. And then slowly adding 100 parts of deionized water, raising the temperature to about 98 ℃, stirring for 20 min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant so that the solution becomes bright yellow. And then centrifugally separating the graphite oxide suspension at the rotating speed of 5000 r/pm, washing the graphite oxide suspension by using deionized water until the separation liquid is neutral, and freeze-drying to obtain GO.
(2) Preparation of enhancer MPA/KH 567/rGO:
dissolving 6 parts of GO in deionized water, performing ultrasonic dispersion, adding 0.3 part of 3-mercaptopropionic acid into a 50 ℃ water bath, and stirring for reaction for 3 hours, so that part of GO can be modified; heating a water bath to 65 ℃, dissolving 0.4 part of coupling agent KH567 in 20wt% phosphoric acid solution, adding the solution into GO dispersion, stirring and reacting for 4 hours, modifying the residual GO, centrifugally washing to be neutral, and freeze-drying to obtain an enhancer MPA/KH 567/rGO.
(3) Preparing a self-made waterborne epoxy emulsifier:
dissolving 3 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, adding 0.5 part of N, N-methylene bisacrylamide to react with the epoxy resin, adding 0.1 part of potassium persulfate initiator, then slowly dropwise adding 6 parts of hydroxyethyl acrylate, heating and stirring to react so that the hydroxyethyl acrylate is subjected to free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, thereby preparing the waterborne epoxy emulsifier.
(4) Preparation of aqueous epoxy emulsion:
weighing 35 parts of epoxy resin E-44, adding 0.5 part of reinforcing agent MPA/KH567/rGO, stirring and dispersing uniformly in a 1500r/min dispersion machine, adding 10 parts of the aqueous epoxy emulsifier, uniformly mixing in a 2000r/min dispersion machine, slowly dripping 40 parts of deionized water within 30min to complete phase inversion, and preparing the aqueous epoxy emulsion.
(5) Preparation of the waterborne epoxy amino baking varnish:
and adding 35 parts of amino resin and 20 parts of deionized water into the waterborne epoxy emulsion, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.2 part of defoaming agent to finally prepare the waterborne epoxy amino baking paint.
(6) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
Example two
(1) GO is prepared by a modified Hummers method:
a250 ml reaction bottle is assembled in an ice-water bath, 3 parts of graphite powder, 2 parts of sodium nitrate, 40 parts of concentrated sulfuric acid and 20 parts of concentrated nitric acid are uniformly mixed, 10 parts of potassium permanganate is added for several times, the temperature is controlled not to exceed 5 ℃, after stirring for a period of time, the ice bath is removed and the reaction bottle is cooled to room temperature, the reaction bottle is transferred to an electromagnetic water bath kettle, and electromagnetic stirring lasts for 24 hours. And then slowly adding 100 parts of deionized water, raising the temperature to about 98 ℃, stirring for 20 min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant so that the solution becomes bright yellow. And then centrifugally separating the graphite oxide suspension at the rotating speed of 5000 r/pm, washing the graphite oxide suspension by using deionized water until the separation liquid is neutral, and freeze-drying to obtain GO.
(2) Preparation of enhancer MPA/KH 567/rGO:
8 parts of GO is dissolved in deionized water for ultrasonic dispersion, and then 0.4 part of 3-mercaptopropionic acid is added into a water bath kettle at 50 ℃ for stirring reaction for 5 hours, so that part of GO can be modified; heating a water bath to 65 ℃, dissolving 0.6 part of coupling agent KH567 in 20wt% phosphoric acid solution, adding the solution into GO dispersion, stirring and reacting for 6 hours, modifying the residual GO, centrifugally washing to be neutral, and freeze-drying to obtain an enhancer MPA/KH 567/rGO.
(3) Preparing a self-made waterborne epoxy emulsifier:
dissolving 4 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, adding 1 part of N, N-methylene bisacrylamide to react with the epoxy resin, adding 0.1 part of potassium persulfate initiator, then slowly dropwise adding 6 parts of hydroxyethyl acrylate, heating and stirring to react so that the hydroxyethyl acrylate is subjected to free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, thereby preparing the waterborne epoxy emulsifier.
(4) Preparation of aqueous epoxy emulsion:
weighing 40 parts of epoxy resin E-44, adding 1 part of reinforcing agent MPA/KH567/rGO, stirring and dispersing uniformly under a 1500r/min dispersion machine, adding 12 parts of the waterborne epoxy emulsifier, uniformly mixing in a 2000r/min dispersion machine, slowly dripping 40 parts of deionized water within 30min to complete phase inversion, and preparing the waterborne epoxy emulsion.
(5) Preparation of the waterborne epoxy amino baking varnish:
and adding 40 parts of amino resin and 15 parts of deionized water into the waterborne epoxy emulsion, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.3 part of defoaming agent to finally prepare the waterborne epoxy amino baking paint.
(6) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
EXAMPLE III
(1) GO is prepared by a modified Hummers method:
a250 ml reaction bottle is assembled in an ice-water bath, 2 parts of graphite powder, 2 parts of sodium nitrate, 30 parts of concentrated sulfuric acid and 10 parts of concentrated nitric acid are uniformly mixed, 8 parts of potassium permanganate is added for several times, the temperature is controlled not to exceed 5 ℃, after stirring for a period of time, the ice bath is removed and the reaction bottle is cooled to room temperature, the reaction bottle is transferred to an electromagnetic water bath kettle, and electromagnetic stirring lasts for 24 hours. And then slowly adding 100 parts of deionized water, raising the temperature to about 98 ℃, stirring for 20 min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant so that the solution becomes bright yellow. And then centrifugally separating the graphite oxide suspension at the rotating speed of 5000 r/pm, washing the graphite oxide suspension by using deionized water until the separation liquid is neutral, and freeze-drying to obtain GO.
(2) Preparation of enhancer MPA/KH 567/rGO:
dissolving 10 parts of GO in deionized water, performing ultrasonic dispersion, adding 0.5 part of 3-mercaptopropionic acid into a 50 ℃ water bath, and stirring for reaction for 5 hours, so that part of GO can be modified; heating a water bath to 65 ℃, dissolving 0.8 part of coupling agent KH567 in 20wt% phosphoric acid solution, adding the solution into GO dispersion, stirring and reacting for 6 hours, modifying the residual GO, centrifugally washing to be neutral, and freeze-drying to obtain an enhancer MPA/KH 567/rGO.
(3) Preparing a self-made waterborne epoxy emulsifier:
dissolving 5 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, adding 1.5 parts of N, N-methylene bisacrylamide to react with the epoxy resin, adding 0.1 part of potassium persulfate initiator, then slowly dropwise adding 8 parts of hydroxyethyl acrylate, heating and stirring to react so that the hydroxyethyl acrylate is subjected to free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, thereby preparing the waterborne epoxy emulsifier.
(4) Preparation of aqueous epoxy emulsion:
weighing 50 parts of epoxy resin E-44, adding 2 parts of reinforcing agent MPA/KH567/rGO, stirring and dispersing uniformly under a 1500r/min dispersing machine, adding 15 parts of the waterborne epoxy emulsifier, uniformly mixing in a 2000r/min dispersing machine, slowly dripping 50 parts of deionized water within 30min to complete phase inversion, and preparing the waterborne epoxy emulsion.
(5) Preparation of the waterborne epoxy amino baking varnish:
and adding 40 parts of amino resin and 20 parts of deionized water into the waterborne epoxy emulsion, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.5 part of defoaming agent to finally prepare the waterborne epoxy amino baking paint.
(6) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
Comparative example 1
(1) Preparing a self-made waterborne epoxy emulsifier:
dissolving 5 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, adding 1.5 parts of N, N-methylene bisacrylamide to react with the epoxy resin, adding 0.1 part of potassium persulfate initiator, then slowly dropwise adding 8 parts of hydroxyethyl acrylate, heating and stirring to react so that the hydroxyethyl acrylate is subjected to free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, thereby preparing the waterborne epoxy emulsifier.
(2) Preparation of aqueous epoxy emulsion:
weighing 10 parts of epoxy resin E-44, adding 3 parts of the waterborne epoxy emulsifier, uniformly mixing in a dispersion machine with the rotating speed of 2000r/min, and slowly dripping 10 parts of deionized water within 30min to prepare the waterborne epoxy emulsion.
(3) Preparation of the waterborne epoxy amino baking varnish:
and adding 45 parts of amino resin and 20 parts of deionized water into the waterborne epoxy emulsion, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.3 part of defoaming agent to finally prepare the waterborne epoxy amino baking paint.
(4) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
Comparative example No. two
Commercially available waterborne epoxy coatings were purchased. Preparation of a paint film: the composite coating is uniformly coated on the polished iron plate, and the thickness is ensured to be 100 +/-5 mu m.
Comparative example No. three
(1) GO is prepared by a modified Hummers method:
a250 ml reaction bottle is assembled in an ice-water bath, 2 parts of graphite powder, 2 parts of sodium nitrate, 30 parts of concentrated sulfuric acid and 10 parts of concentrated nitric acid are uniformly mixed, 8 parts of potassium permanganate is added for several times, the temperature is controlled not to exceed 5 ℃, after stirring for a period of time, the ice bath is removed and the reaction bottle is cooled to room temperature, the reaction bottle is transferred to an electromagnetic water bath kettle, and electromagnetic stirring lasts for 24 hours. And then slowly adding 100 parts of deionized water, raising the temperature to about 98 ℃, stirring for 20 min, and adding a proper amount of hydrogen peroxide to reduce the residual oxidant so that the solution becomes bright yellow. And then centrifugally separating the graphite oxide suspension at the rotating speed of 5000 r/pm, washing the graphite oxide suspension by using deionized water until the separation liquid is neutral, and freeze-drying to obtain GO.
(2) Preparing a self-made waterborne epoxy emulsifier:
dissolving 5 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, adding 1.5 parts of N, N-methylene bisacrylamide to react with the epoxy resin, adding 0.1 part of potassium persulfate initiator, then slowly dropwise adding 8 parts of hydroxyethyl acrylate, heating and stirring to react so that the hydroxyethyl acrylate is subjected to free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, thereby preparing the waterborne epoxy emulsifier.
(3) Preparation of aqueous epoxy emulsion:
weighing 50 parts of epoxy resin E-44, adding 2 parts of GO, stirring and dispersing uniformly in a 1500r/min dispersion machine, adding 15 parts of the aqueous epoxy emulsifier, uniformly mixing in a 2000r/min dispersion machine, and slowly dripping 50 parts of deionized water within 30min to prepare the aqueous epoxy emulsion.
(4) Preparation of the waterborne epoxy amino baking varnish:
and adding 40 parts of amino resin and 20 parts of deionized water into the waterborne epoxy emulsion, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.5 part of defoaming agent to finally prepare the waterborne epoxy amino baking paint.
(5) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
Paint film test performance table:
the water-based epoxy amino baking paint film prepared by the self-made emulsifier and the performance of the water-based epoxy amino baking paint film can be seen from the table, the water-based epoxy amino baking paint film prepared by the self-made emulsifier and the performance of the water-based epoxy resin emulsion sold in the market are seen from the table, the performance of the water-based epoxy resin emulsion baked paint film prepared by the self-made emulsifier is better than that of the water-based epoxy resin emulsion sold in the market in chemical corrosion resistance and weather resistance, and the emulsion prepared by the emulsifier is proved to have improved crosslinking density and tighter crosslinking and be capable of blocking the contact of a corrosion medium and an iron substrate for a longer time.
And in the third comparative example, only graphene is added as a reinforcing agent and added into the waterborne epoxy amino baking paint, compared with the first comparative example, the performance of the paint film is improved to a certain extent, which proves that the graphene plays a certain role in blocking the paint film, and the performance of the paint film is improved due to the labyrinth effect.
The reinforcing agent used in the second, third and fourth embodiments is the reinforcing agent MPA/KH567/rGO prepared by the method, the chemical corrosion resistance, salt fog resistance, hardness and adhesion performance of the second, third and fourth embodiments are improved, the corrosion resistance of the second embodiment is relatively good with the increasing of the addition amount, the addition amount is moderate, too little reinforcing agent cannot play an effective corrosion resistance role, and too much reinforcing agent is added, so that the agglomeration of the reinforcing agent in the cross-linking process of a paint film is easily caused, and the performance of the paint film is influenced by defects.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. An MPA/KH567/rGO reinforced waterborne epoxy amino baking paint is characterized by comprising the following raw materials in parts by weight:
10-15 parts of water-based epoxy emulsifier
30-50 parts of epoxy resin
35-40 parts of amino resin
0.5-2 parts of reinforcing agent
0.1 to 0.5 portion of defoaming agent
40-70 parts of deionized water
The preparation method of the water-based epoxy emulsifier comprises the following steps: dissolving epoxy resin E-44 in a solvent, adding N, N-methylene bisacrylamide to react with the epoxy resin E-44, adding hydroxyethyl acrylate after the reaction is finished, adding a small amount of initiator potassium persulfate, heating and stirring to enable the hydroxyethyl acrylate to undergo free radical polymerization to form epoxy resin-polyhydroxyethyl acrylate, namely the waterborne epoxy emulsifier.
2. The waterborne epoxy amino baking varnish according to claim 1, wherein the reinforcing agent is MPA/KH567/rGO, and is prepared by the following steps: graphene oxide GO is prepared by a modified Hummers method, GO is dissolved in water and subjected to ultrasonic dispersion, part of GO is modified after being added with 3-mercaptopropionic acid and stirred to react, KH567 is dissolved by using a 20wt% phosphoric acid solution, the rest GO is added into a GO dispersion liquid to be modified, the mixture is centrifugally washed to be neutral, and an enhancer MPA/KH567/rGO is obtained after freeze-drying.
3. The waterborne epoxy amino baking varnish according to claim 1, wherein the amino resin has an active hydrogen equivalent of 400 to 430.
4. The waterborne epoxy amino baking varnish according to claim 1, wherein the defoamer is a BYK silicone defoamer.
5. The preparation method of the water-based epoxy baking paint as claimed in claim 1, wherein the epoxy resin and the reinforcing agent are uniformly dispersed in a dispersion machine at a rotation speed of 1000r/min, the water-based epoxy emulsifier is added, then the deionized water is slowly dripped to complete phase inversion to prepare the water-based epoxy emulsion, the amino resin and the deionized water are uniformly mixed, the defoaming agent is added, and the mixture is dispersed for 30min under the condition of the dispersion machine at a rotation speed of 1500r/min to obtain the water-based epoxy amino baking paint.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113502139A (en) * | 2021-08-27 | 2021-10-15 | 北京市建筑工程研究院有限责任公司 | Low-temperature-resistant slow-bonding prestressed tendon |
| CN113881308A (en) * | 2021-09-22 | 2022-01-04 | 无锡绿环交通科技有限公司 | Single-component second-order reaction water-based epoxy closed emulsion for bridge deck concrete |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038487A (en) * | 2015-07-26 | 2015-11-11 | 青岛金日来石墨有限公司 | Water-based anticorrosive paint for ship and preparation method of water-based anticorrosive paint |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038487A (en) * | 2015-07-26 | 2015-11-11 | 青岛金日来石墨有限公司 | Water-based anticorrosive paint for ship and preparation method of water-based anticorrosive paint |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113502139A (en) * | 2021-08-27 | 2021-10-15 | 北京市建筑工程研究院有限责任公司 | Low-temperature-resistant slow-bonding prestressed tendon |
| CN113502139B (en) * | 2021-08-27 | 2022-10-04 | 北京市建筑工程研究院有限责任公司 | Low-temperature-resistant slow-bonding prestressed tendon |
| CN113881308A (en) * | 2021-09-22 | 2022-01-04 | 无锡绿环交通科技有限公司 | Single-component second-order reaction water-based epoxy closed emulsion for bridge deck concrete |
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