CN113174183B - Organic solvent-free graphene-reinforced waterborne epoxy resin coating and preparation method thereof - Google Patents
Organic solvent-free graphene-reinforced waterborne epoxy resin coating and preparation method thereof Download PDFInfo
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- CN113174183B CN113174183B CN202110462218.9A CN202110462218A CN113174183B CN 113174183 B CN113174183 B CN 113174183B CN 202110462218 A CN202110462218 A CN 202110462218A CN 113174183 B CN113174183 B CN 113174183B
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- C—CHEMISTRY; METALLURGY
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- 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
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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Abstract
The invention discloses an organic solvent-free graphene-reinforced aqueous epoxy resin coating and a preparation method thereof. In the process, amino and ionic sites can be introduced by using the methylene bisacrylamide, and then an acrylate monomer is introduced through free radical polymerization and enters an emulsifier molecular chain, and the dispersion stability of the emulsion is improved by introducing a polypropylene glycol chain segment. The invention solves the problems of uncontrollable emulsifier synthesis process, large viscosity, uneven reaction, influence on water resistance and the like, solves the limitation that an organic solvent must be added in emulsifier synthesis, realizes the purpose of preparing the emulsifier without any volatile organic solvent, and the obtained graphene reinforced water-based epoxy resin coating has excellent mechanical property and corrosion resistance.
Description
Technical Field
The invention belongs to the field of waterborne epoxy coatings, and particularly relates to an organic solvent-free graphene-reinforced waterborne epoxy resin coating and a preparation method thereof.
Background
With the rapid increase of economy in China, the demand and the yield of various industrial products are increased year by year, and the environment, the health, the resources and the like are tested. With the corresponding departure of various regulations, it has become increasingly important to control the use of volatile organic compounds. In the field of paints, there is a trend that water-based paints using water as a solvent or a dispersion medium are partially used instead of oil-based paints using volatile organic compounds as a solvent.
The epoxy resin is a kind of polymer with main chain containing two or more epoxy groups, and is a kind of thermosetting resin, and the epoxy groups can be opened by amino groups and other groups containing active hydrogen, and cured to form a net structure. The epoxy resin contains various polar groups such as hydroxyl groups and the like in the molecule, so that the epoxy resin has excellent adhesion. And after being cured, the resin has stable size and good weather resistance, and is often used as matrix resin of various anticorrosive coatings.
In the existing water-based epoxy resin, the particle size of a dispersed phase of the water-based epoxy resin prepared by a phase inversion method of mixing a synthetic emulsifier with the epoxy resin and adding water for stirring is small, the epoxy resin is dispersed in the water phase in the form of emulsion particles, partial advantages of the traditional solvent-based epoxy resin coating can be reserved, the content of volatile organic matters is low, and the water-based epoxy resin has a high development space. However, the nonionic emulsifier has poor emulsion stability, and needs to be used in combination with an ionic emulsifier, and the nonionic emulsifier has a serious influence on the water resistance of the emulsion. For ionic emulsifier, the viscosity is high and the reaction is not uniform due to the action of intermolecular hydrogen bond and van der waals force in the synthetic process, and the crosslinking deterioration is easy to generate, so that an organic solvent is required to be added in the synthetic process. The organic solvent added in the process must be separated by techniques such as distillation, or else the emulsion effect is obviously influenced and the VOC emission is increased along with the entering of the emulsifier into the epoxy resin system.
Acrylic monomers are widely applied to the field of coatings, wherein part of acrylate monomers have water-oil amphipathy, and free radical polymerization can be carried out between acrylates to generate macromolecules, so that the acrylate monomers are harmless to the environment. Related researches have proved that acrylic monomers can be grafted on epoxy resin under certain conditions, which provides a new idea for realizing solvent-free synthesis of epoxy resin emulsifier. The methylene bisacrylamide has a special structure (not only contains carbon-carbon double bonds, but also contains secondary amine groups), and the methylene bisacrylamide is introduced to the acrylic acid chain segment, so that an unreacted emulsifier can be changed into a reactive cationic emulsifier, the crosslinking density is obviously improved, and the water resistance is improved.
Graphene has good electrical and thermal conductivity and excellent mechanical properties, but graphene itself has hydrophobicity and lipophilicity, and is good in solubility in a nonpolar solvent, but can agglomerate in water to affect the applicability of the graphene, which limits the use of the graphene in an aqueous coating.
Disclosure of Invention
Aiming at the defect that a solvent type coating contains more volatile organic compounds which are not friendly to the environment and human body, the invention provides an organic solvent-free graphene-reinforced water-based epoxy resin coating, which is prepared by mainly introducing ionic groups into low-molecular-weight epoxy resin through reaction, removing acrylic ester serving as a solvent through free radical polymerization and grafting, simultaneously introducing methylene bisacrylamide to obtain a cationic water-based epoxy resin emulsifier, and dispersing graphene by using the emulsifier and matching the graphene with epoxy resin and a curing agent to obtain the coating with excellent performance. Volatile organic solvents and graphene dispersing agents are not added in the preparation process, so that the water resistance of the dried coating is improved, and the excellent protective performance of the epoxy resin is kept.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic solvent-free graphene-reinforced waterborne epoxy resin coating is prepared by the following steps:
1) under the condition of taking acrylic ester as a solvent, reacting excessive ethanolamine with low molecular weight epoxy resin to introduce active hydrogen and a cationic chain segment, then adding a neutralizing agent, water, polypropylene glycol diglycidyl ether and methylene bisacrylamide to perform copolymerization reaction, heating, and then adding an initiator to perform free radical polymerization and grafting reaction to obtain a cationic waterborne epoxy resin emulsifier;
the specific operation is as follows: adding 2g of acrylate into a three-neck flask provided with a stirrer and a water bath, then adding 1.35g of ethanolamine, heating to 50 ℃ under the stirring condition of 200r/min to uniformly mix the system, then adding 5g of low molecular weight epoxy resin, continuously stirring at the speed of 200r/min for 10min, heating to 60 ℃, then carrying out heat preservation reaction for 2h, then sequentially adding 0.5g of neutralizing agent, 15g of water, 11g of polypropylene glycol diglycidyl ether and 3.4g of methylene bisacrylamide, continuously stirring at the speed of 200r/min, carrying out heat preservation reaction for 2h, then adding 0.2g of initiating agent, simultaneously heating to 95 ℃, continuously stirring at the speed of 200r/min for reaction for 8h, and obtaining a cationic waterborne epoxy resin emulsifier;
2) and mixing the obtained cationic waterborne epoxy resin emulsifier with low-molecular-weight waterborne epoxy resin, a neutral waterborne epoxy resin curing agent and graphene in proportion to obtain the graphene-reinforced waterborne epoxy resin coating.
The neutralizing agent in the step 1) is any one of glacial acetic acid and acrylic acid. The initiator is any one of ammonium persulfate, potassium persulfate, azobisisobutyronitrile and benzoyl peroxide.
The raw materials used in the step 2) are as follows according to parts by weight: 54.5-54.7 parts of cationic waterborne epoxy resin emulsifier, 15 parts of low molecular weight waterborne epoxy resin, 0.3-0.5 part of graphene and 30 parts of neutral waterborne epoxy resin curing agent.
The graphene is preferably prepared by a ball milling method. Compared with graphene prepared by a redox method, the preparation process of graphene by a ball milling method is simpler and more environment-friendly. The graphene has few oxygen-containing functional groups on the surface, is strong in hydrophobicity, and well retains the characteristics of graphene.
The invention has the advantages that:
1. compared with the prior patents, the cationic waterborne epoxy resin emulsifier provided by the invention does not add any additional organic solvent in the synthesis process, and the reaction is uniform; the methylene bisacrylamide is used for introducing secondary amine groups into the synthetic emulsifier, so that the emulsifier has reactivity, and the mechanical property of a paint film is improved; the process of taking the acrylic ester as the solvent for final reaction and entering the product is innovative, and the problem of removing the solvent after synthesis is solved.
2. Compared with the prior patents, the graphene can be dispersed in water without modification treatment and addition of a special dispersant, so that the excellent barrier property of the graphene can be fully exerted and the performance of a paint film is not influenced.
3. According to the invention, the cationic emulsifier is used for assisting in dispersing graphene, so that the introduction of a small molecular active agent can be avoided, the structural damage of a paint film can be prevented, and the water resistance is maintained.
Drawings
FIG. 1 is a Tafel polarization curve of a paint film obtained by soaking a commercial graphene coating (left) and a composite coating (right) of the invention in 3.5wt% saline water. The Tafel curve can reflect the strength of the corrosion protection capability of the coating on the substrate, and as can be seen from the figure, when the reference electrode uses a saturated calomel electrode, the open-circuit potential of the composite coating is increased relative to that of the commercially available graphene coating, and the polarization current is reduced under the same potential difference, which indicates that the resistance of the coating is higher than that of the commercially available graphene coating. Therefore, according to fitting, the self-corrosion current of the coating is obviously smaller than that of the commercial graphene coating, and the coating is proved to have higher corrosion resistance.
FIG. 2 is a comparison graph of paint films obtained from a commercial graphene coating (left) and a composite coating (right) of the invention after a 10d salt spray experiment. As shown in fig. 2, both coatings corroded, but the inventive coatings corroded to a significantly lesser degree than the commercially available graphene coatings, indicating better protection.
Detailed Description
In order to make the content of the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Synthesizing a cationic water-based epoxy resin emulsifier: adding 2g of acrylate into a three-neck flask provided with a stirrer and a water bath, then adding 1.35g of ethanolamine, heating to 50 ℃ under the stirring condition of 200r/min to uniformly mix the system, then adding 5g of low molecular weight epoxy resin E-44, continuing stirring at the speed of 200r/min for 10min, heating to 60 ℃, then carrying out heat preservation reaction for 2h, then sequentially adding 0.5g of glacial acetic acid, 15g of water, 11g of polypropylene glycol diglycidyl ether and 3.4g of methylene bisacrylamide, continuing stirring at the speed of 200r/min, carrying out heat preservation reaction for 2h, then adding 0.2g of azobisisobutyronitrile into the three-neck flask, simultaneously heating to 95 ℃, and then carrying out stirring reaction at the speed of 200r/min for 8h to obtain the cationic water-based epoxy resin emulsifier.
The active hydrogen equivalent of the neutral water-based epoxy resin curing agent is 400-450.
The low molecular weight waterborne epoxy resin used was E-44.
The graphene is prepared by a ball milling method, and is specifically prepared by performing high-speed ball milling on natural flake graphite for more than 48 hours, and centrifuging, cleaning and drying supernatant; the number of layers is less than 20, and the size of the sheet layer is less than 10 microns.
Example 1
Preparing the composite coating: 5.47g of cationic waterborne epoxy resin emulsifier, E-441.5 g of epoxy resin, 0.3g of graphene and 3g of waterborne epoxy resin curing agent are stirred for 30min at normal temperature at the rotating speed of 500r/min to obtain the composite coating.
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.
Example 2
Preparing the composite coating: and (3) taking 5.46g of cationic waterborne epoxy resin emulsifier, E-441.5 g of epoxy resin, 0.4g of graphene and 3g of waterborne epoxy resin curing agent, and stirring at normal temperature at the rotating speed of 500r/min for 30min to obtain the composite coating.
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.
Example 3
Preparing the composite coating: 5.45g of cationic waterborne epoxy resin emulsifier, E-441.5 g of epoxy resin, 0.5g of graphene and 3g of waterborne epoxy resin curing agent are stirred for 30min at normal temperature at the rotating speed of 500r/min to obtain the composite coating.
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 1
Preparation of a blank coating: 6g of waterborne epoxy resin curing agent and 3g of waterborne epoxy resin (the waterborne epoxy resin is prepared by a non-ionic emulsifier and epoxy resin E-44 through a phase inversion method) are uniformly stirred to obtain the blank coating.
Preparation of a paint film: and uniformly coating the blank paint on the polished iron plate, and ensuring the thickness to be 100 +/-5 mu m.
Comparative example 2
Commercially available waterborne UV light curable coatings. The solid content is about 50 percent, the content of the maleic anhydride modified self-emulsifying waterborne epoxy resin is 50 percent by weight, and the waterborne emulsion is matched with deionized water.
Preparation of a paint film: the waterborne UV photocureable coating is uniformly coated on a polished iron plate, and the thickness is ensured to be 100 +/-5 mu m.
Comparative example 3
Commercially available aqueous graphene coatings. The solid content is about 50%, the graphene content is 2wt%, and the acrylic acid modified water-based resin and additive content is 48 wt%.
Preparation of a paint film: and uniformly coating the water-based graphene coating on the polished iron plate, and ensuring the thickness to be 100 +/-5 microns.
The paint films obtained in the examples and comparative examples were subjected to performance tests, and the results thereof are shown in Table 1.
TABLE 1 results of property tests on paint films obtained in examples and comparative examples
As can be seen from Table 1, the examples show better performance than the comparative examples. As can be seen from examples 1, 2, 3, as the content of graphene increases, the tensile strength of the resulting paint film decreases, barrier properties increase, and adhesion is also affected. Based on this, comparing the examples and the comparative example 1, it can be seen that the tensile strength and the bending strength of the examples are all stronger than those of the comparative example 1, and the addition of the methylene bisacrylamide is proved to obviously improve the tensile strength and the bending strength. In a similar way, the flexibility of the paint film can be reduced by introducing the graphene, and the flexibility of different resins is close to that of the paint film under the condition that the addition amount of the main film forming matter is close to that of the components, so that the flexibility of the embodiment is higher than that of the comparative example 2, and the introduction of the polypropylene glycol chain segment obviously improves the flexibility of the paint film.
The mechanical properties of the paint films obtained in the examples and comparative examples were measured after soaking the films in 3.5wt% saline for 3 days, and the results are shown in Table 2.
TABLE 2 measurement results of mechanical properties of paint films obtained in examples and comparative examples
As can be seen from Table 2, after soaking, the properties of the commercially available coating are significantly reduced compared to the example coatings, indicating that the coating of the present invention has higher stability of properties.
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 (4)
1. A preparation method of an organic solvent-free graphene-reinforced water-based epoxy resin coating is characterized by comprising the following steps:
1) under the condition of taking acrylic ester as a solvent, reacting excessive ethanolamine with low-molecular-weight epoxy resin, then adding a neutralizing agent, water, polypropylene glycol diglycidyl ether and methylene bisacrylamide for copolymerization reaction, heating, and then adding an initiator for free radical polymerization and graft reaction to obtain a cationic waterborne epoxy resin emulsifier;
2) mixing the obtained cationic waterborne epoxy resin emulsifier with low-molecular-weight waterborne epoxy resin, a neutral waterborne epoxy resin curing agent and graphene in proportion to obtain the graphene-reinforced waterborne epoxy resin coating;
the specific preparation steps of the cationic waterborne epoxy resin emulsifier in the step 1) are as follows: adding 1.35g of ethanolamine into 2g of acrylate, heating to 50 ℃ under the stirring condition of 200r/min to uniformly mix the system, adding 5g of low molecular weight epoxy resin, continuously stirring at the speed of 200r/min for 10min, heating to 60 ℃, then carrying out heat preservation reaction for 2h, sequentially adding 0.5g of neutralizing agent, 15g of water, 11g of polypropylene glycol diglycidyl ether and 3.4g of methylene bisacrylamide, continuously stirring at the speed of 200r/min, carrying out heat preservation reaction for 2h, then adding 0.2g of initiator, simultaneously heating to 95 ℃, and then continuously stirring at the speed of 200r/min for reaction for 8h to obtain the acrylic ester;
the raw materials used in the step 2) are as follows according to parts by weight: 54.5-54.7 parts of cationic waterborne epoxy resin emulsifier, 15 parts of low molecular weight waterborne epoxy resin, 0.3-0.5 part of graphene and 30 parts of neutral waterborne epoxy resin curing agent.
2. The method for preparing the organic solvent-free graphene-reinforced water-based epoxy resin coating according to claim 1, wherein the neutralizing agent is any one of glacial acetic acid and acrylic acid.
3. The method for preparing the organic solvent-free graphene-reinforced water-based epoxy resin coating according to claim 1, wherein the initiator is any one of ammonium persulfate, potassium persulfate, azobisisobutyronitrile and benzoyl peroxide.
4. An organic solvent-free graphene-reinforced waterborne epoxy resin coating prepared according to the method of claim 1.
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