CN109233390B - Environment-friendly epoxy resin coating for buildings - Google Patents

Environment-friendly epoxy resin coating for buildings Download PDF

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CN109233390B
CN109233390B CN201811003181.8A CN201811003181A CN109233390B CN 109233390 B CN109233390 B CN 109233390B CN 201811003181 A CN201811003181 A CN 201811003181A CN 109233390 B CN109233390 B CN 109233390B
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CN109233390A (en
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不公告发明人
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Ganzhou zhenniu waterproof building materials Co., Ltd
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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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention discloses an environment-friendly epoxy resin coating for buildings, which is prepared by using bisphenol A epoxy resin modified by high-temperature glass flakes as a base material and various fillers or assistants such as environment-friendly silica gel fillers, toughening agents and the like, has no solvent residue, is environment-friendly and low in toxicity as raw materials, can uniformly disperse the fillers, and comprises the following raw materials in parts by weight: 60-90 parts of modified epoxy resin matrix material, 12-18 parts of environment-friendly silica gel filler, 6-15 parts of epoxy active diluent, 8-13 parts of core-shell structure toughening agent, 4-8 parts of sodium methylene dinaphthalenesulfonate and carbon black-SiO22-6 parts of double nano filler, 3-8 parts of polydimethylsiloxane and 32-58 parts of deionized water, wherein the preparation method comprises the steps of nano slurry preparation, component A preparation and mixed material oscillation. The environment-friendly epoxy resin coating for buildings has good weather resistance, salt mist resistance and wear resistance, and is suitable for being used as a coating for external walls or internal walls of buildings.

Description

Environment-friendly epoxy resin coating for buildings
Technical Field
The invention relates to the technical field of water-based building coatings, in particular to an environment-friendly epoxy resin coating for buildings.
Background
In the prior art, in order to protect buildings, the coating should be designed according to the use environment, the building category and the substrate characteristics, for example, in order to improve the wear resistance of wooden buildings, the related coating should have certain wear resistance characteristics. The epoxy resin coating is prepared by taking epoxy resin as a main component and matching with various fillers, additives and solvents, and has excellent bonding performance, wear resistance and corrosion resistance. According to the use performance, the coating is generally divided into wear-resistant epoxy coating, anticorrosion epoxy coating, antistatic epoxy coating and architectural decoration epoxy coating.
The epoxy coating for architectural decoration is generally prepared by using high-molecular epoxy resin, a toughening agent, a leveling agent, talcum powder white carbon black filler, a curing agent and an organic solvent according to a specific proportion. It mainly has the following problems: (1) the organic solvent in the formula usually adopts a solution with medium polarity such as toluene, benzene, ethyl acetate and the like, has good solubility on epoxy resin and an auxiliary agent, is beneficial to molecular diffusion, but a certain amount of solvent always remains in the coating along with the volatilization of the solvent in the film forming process, especially after the coating is cured at room temperature, the volatilization speed is extremely slow, and the residue can be detected after years; (2) the fillers such as talcum powder and white carbon black cannot be uniformly dispersed in the coating, so that the cohesive force of the product is reduced, the product is easy to crack and fall off when being invaded by moisture and chemical substances, and the corrosion resistance and the wear resistance are influenced; (3) according to the interpretation of the latest standard of HJ2537-2014 'environmental standard product technical requirement water paint', phthalic acid esters, glycol ethers, halogenated hydrocarbons, toluene, xylene and other substances harmful to human beings cannot be artificially added into the water paint, the glycol ethers and esters thereof cannot exceed 100mg/kg, the prior paint usually adopts waste phthalate as a plasticizing softener, and the glycol ethers as a surfactant are strictly controlled. In conclusion, the existing epoxy coating for architectural decoration has the problems of difficult solvent volatilization, high solvent residual toxicity, insufficient environmental protection of raw materials, nonuniform dispersion of fillers and the like.
The Chinese patent publication No. CN104910759A discloses a water-based epoxy coating and a preparation method thereof, the coating comprises amino resin, a flatting agent, distilled water, water-based epoxy acrylic resin, a dispersing agent, a defoaming agent, iron black, superfine talcum powder, precipitated barium sulfate, zinc phosphate, an antirust agent and the like, and further nano MoS is added2Wear-resisting agent and nano CaCO3The ultraviolet absorber is used for improving the performance, and the coating has excellent water resistance, ultraviolet resistance and salt spray resistance. But in the nano MoS2The preparation process of the wear-resisting agent uses highly toxic CCl4And specific components of a leveling agent, a dispersing agent, a defoaming agent and an antirust agent are not disclosed, so that the repeatability is poor, and the requirements of environment-friendly epoxy resin coatings are not met.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide an environment-friendly epoxy resin coating for buildings, which is prepared by using bisphenol A epoxy resin modified by high-temperature glass flakes as a base material and various fillers or additives such as environment-friendly silica gel fillers, epoxy active diluents, toughening agents and the like, has no solvent residue, is environment-friendly and low in toxicity as a raw material, can uniformly disperse the fillers, has good weather resistance, salt mist resistance and wear resistance, and is suitable for being used as a building exterior wall coating or interior wall coating.
The purpose of the invention can be realized by the following technical scheme:
the invention provides an environment-friendly epoxy resin coating for buildings, which comprises the following raw materials in parts by weight: 60-90 parts of modified epoxy resin matrix material, 12-18 parts of environment-friendly silica gel filler, 6-15 parts of epoxy active diluent, 8-13 parts of core-shell structure toughening agent, 4-8 parts of methylene dinaphthalene sodium sulfonate, 2-6 parts of carbon black-SiO 2 double nano filler, 3-8 parts of polydimethylsiloxane and 32-58 parts of deionized water;
the modified epoxy resin matrix material comprises the following raw materials in parts by weight: 70 parts of bisphenol A type epoxy resin, 15 parts of high-temperature glass flakes, 6 parts of nano zirconia, 2 parts of graphene oxide and 110 parts of dimethyl carbonate; the preparation method of the modified epoxy resin matrix material comprises the following steps:
1) adding bisphenol A epoxy resin and dimethyl carbonate into a high-speed dispersion machine, and heating to 105 ℃ to completely dissolve the bisphenol A epoxy resin;
2) sequentially adding high-temperature glass flakes, nano zirconia and graphene oxide into the system in the step 1), and dispersing and homogenizing at a high speed to form a stable dispersion;
3) introducing the dispersion into a high-pressure homogenizer, homogenizing under 8MPa to obtain a mixed material, placing the mixed material on a hot-pressing mold, hot-pressing at 100 deg.C and 1.2MPa for 80s for molding, cooling to room temperature, solidifying at 150 deg.C for 50min, and pulverizing into matrix material with particle size of 50-100 μm by an ultrafine pulverizer.
In the screening and selection of the raw materials of the environment-friendly epoxy resin coating, the traditional epoxy resin has strong cohesiveness and poor compatibility of the filler, and the raw materials contain toxic compounds such as phthalate, glycol ether and low-toxicity organic solvents, so that the environment-friendly epoxy resin coating does not meet the requirement of environmental protection, is easy to pulverize and crack after being subjected to long-term sun and rain exposure and chemical corrosion, reduces the cohesiveness of the coating and reduces the wear resistance.
The inventor selects low-viscosity and low-molecular-weight bisphenol A epoxy resin, and discovers that after the addition of high-temperature glass flakes, nano-zirconia and graphene oxide and the selection of a green environment-friendly solvent dimethyl carbonate through a large number of screening and experiments, the bisphenol A epoxy resin has good heat resistance and impact toughness on the basis of improving the wear resistance. Through the analysis of the mechanism, the high-temperature glass flakes have a larger extension coefficient compared with epoxy resin, the bisphenol A epoxy resin is easy to crack and fall off under the conditions of dispersion and hot pressing, and the high-temperature glass flakes can form a thermal stable layer, so that the high-temperature glass flakes are not easy to expand by heating and have good compatibility; dispersing nano titanium dioxide serving as a dispersed phase of micromolecules into bisphenol A type epoxy resin with a heat stabilizing layer to strengthen and toughen the bisphenol A type epoxy resin; the graphene oxide with amphipathy shows the property distribution from hydrophilicity to hydrophobicity from the edge to the center, and is like the surfactant dispersed in bisphenol A type epoxy resin, so that the energy between molecular interfaces is reduced, the modified epoxy resin matrix material keeps the balance between the hydrophobicity and the hydrophilicity, meanwhile, the toughness is enhanced, and the mechanical property and the temperature resistance are obviously improved.
As a further scheme of the invention, the environment-friendly silica gel filler comprises the following raw materials in parts by weight: 125 parts of fluorosilicone raw rubber, 8 parts of hydroxyl silicone oil, 3.6 parts of glass fiber, 1.2 parts of montmorillonite, 0.3 part of nano zinc oxide and 0.16 part of sodium dodecyl sulfate; the specific preparation method of the environment-friendly silica gel filler comprises the following steps:
1) weighing glass fiber, montmorillonite and nano zinc oxide according to the weight parts, sequentially adding the glass fiber, the montmorillonite and the nano zinc oxide into a reaction kettle, and blending at a high speed for 20min to obtain a reinforcing filler mixture;
2) adding the fluorosilicone crude rubber, the hydroxyl silicone oil and the sodium dodecyl sulfate into an internal mixer for internal mixing for 40min to ensure complete fusion to obtain a mixture A;
3) slowly adding the reinforcing filler mixture of 1/3 into the mixture A, heating to 40 ℃, stirring at the rotating speed of 400r/min for 20min, adding the rest reinforcing filler 2/3, heating to 50 ℃, and stirring at 300r/min for 35min to obtain a silica gel mixture;
4) introducing the silica gel mixture into a kneading machine, kneading and molding, feeding into a molding machine, molding at 180 ℃ for 12min, and cooling to normal temperature.
In the research process of the raw material screening and preparation method of the environment-friendly silica gel filler, the invention selects the reinforcing filler glass fiber, the montmorillonite and the nano zinc oxide to stabilize the strength and the elasticity of the fluorosilicone raw rubber and further improve the tear resistance of the fluorosilicone raw rubber. Experiments show that the addition of the glass fiber can keep the fluorosilicone raw rubber to have good elasticity in long-term use and has the function of keeping the elasticity uniformity. In addition, the glass fiber belongs to inorganic fiber which is nontoxic and easy to be compatible with organic matters, and can be uniformly dispersed in the fluorine-silicon crude rubber. Montmorillonite as a reinforcing substance for enhancing the tearing strength can permeate into a macromolecular cross-linked structure of the fluorosilicone raw rubber, so that the tendency of gradual tearing along a cracking opening is effectively prevented, and the problem of serious aging phenomenon of the coating after cracking is effectively reduced. In the preparation method, the raw materials of the silica gel filler can be fully melted and dispersed by high-speed dispersion and banburying, and the compatibility with the modified epoxy resin matrix material is better.
As a further scheme of the invention, the epoxy reactive diluent is prepared by mixing ethylene carbonate, propylene carbonate and benzyl alcohol according to the mass ratio of 3:1: 1.
As a further aspect of the present invention, the core-shell structure toughening agent is selected from an MBS type toughening agent or an ACR type toughening agent.
As a further aspect of the present invention, the carbon black-SiO2The double nano filler is prepared by uniformly mixing carbon black and silica gel with pH of 7 according to the mass ratio of 1:8-10, precipitating for 24h, washing with ethanol, performing vacuum filtration, and performing sterile drying at 55 ℃.
As a further scheme of the invention, the preparation method of the environment-friendly epoxy resin coating for buildings comprises the following steps:
1) preparing nano slurry: adding the environment-friendly silica gel filler and the carbon black-SiO 2 double nano filler into a dispersion machine, dropwise adding an epoxy active diluent in the stirring process, dispersing at a high speed for 50min, and then ultrasonically oscillating for 30min to form nano slurry with the fineness less than 200 nm;
2) preparation of component A: adding the modified epoxy resin matrix material and the sodium methylenedinaphthalene sulfonate into a high-speed dispersion kettle for dispersion for 20min, adding the core-shell structure toughening agent, feeding into a ball mill for dry ball milling for 45min, and filtering under reduced pressure to obtain a component A;
3) mixing and oscillating: under the condition of normal temperature, mixing the nano slurry, the component A, the polydimethylsiloxane and the deionized water, adding the mixture into an ultrasonic oscillator, and carrying out ultrasonic treatment for 8min at the frequency of 40-60KHZ to obtain the environment-friendly epoxy resin coating.
In the preparation method of the environment-friendly epoxy resin coating for buildings, environment-friendly silica gel filler and carbon black-SiO are selected2The double nano-fillers and the epoxy active diluent are dispersed and oscillated to generate nano-slurry, and the epoxy active diluent formed by mixing ethylene carbonate, propylene carbonate and benzyl alcohol can directly participate in the curing reaction of epoxy resin and has good compatibility, so the rest two fillers are mixed and ground firstly, and the granularity is reduced; then carrying out dry ball milling on the modified epoxy resin matrix material, excellent diffusion water reducing agent methylene dinaphthalene sodium sulfonate and core-shell structure toughening agent to obtain a component A, wherein no organic solvent is added in the ball milling process, so that the problem of solvent residue is avoided, and meanwhile, in the grinding process, the diffusion of the water reducing agent and the toughening agent and the combination of the water reducing agent and the modified epoxy resin matrix material are facilitated; in the final step of preparation, simple mixing and stirring in the traditional method are not adopted, but ultrasonic oscillation and stirring are carried out by using an ultrasonic oscillator, and the impact dispersion of the nano slurry and the component A can be promoted by using ultrasonic with specific frequency, so that the proper viscosity and dispersion degree can be conveniently adjusted, and the coating is beneficial to brush coating or roller coating construction.
The invention has the beneficial effects that:
1. the environment-friendly epoxy resin coating for buildings is prepared by using bisphenol A epoxy resin modified by high-temperature glass flakes as a base material and various fillers or auxiliaries such as environment-friendly silica gel fillers, epoxy active diluents, toughening agents and the like, has no solvent residue, is environment-friendly and low in toxicity as raw materials, can uniformly disperse the fillers, has good weather resistance, salt mist resistance and wear resistance, and is suitable for being used as building exterior wall or interior wall coatings.
2. In the modified epoxy resin matrix material, the high-temperature glass flakes have a larger extension coefficient than epoxy resin, bisphenol A epoxy resin is easy to crack and fall off under the conditions of dispersion and hot pressing, and the high-temperature glass flakes can form a thermal stable layer, so that the high-temperature glass flakes are not easy to expand by heating and have good compatibility; dispersing nano titanium dioxide serving as a dispersed phase of micromolecules into bisphenol A type epoxy resin with a heat stabilizing layer to strengthen and toughen the bisphenol A type epoxy resin; the graphene oxide is dispersed in the bisphenol A epoxy resin like a surfactant, so that the energy between molecular interfaces is reduced, the modified epoxy resin matrix material keeps the balance between hydrophobicity and hydrophilicity, the toughness is enhanced, and the mechanical property and the temperature resistance are obviously improved.
3. In the preparation method of the environment-friendly epoxy resin coating for buildings, the epoxy active diluent formed by mixing ethylene carbonate, propylene carbonate and benzyl alcohol can directly participate in the curing reaction of epoxy resin, and has good compatibility, so that two fillers are mixed and ground firstly, and the granularity is reduced; then carrying out dry ball milling on the modified epoxy resin matrix material, excellent diffusion water reducing agent methylene dinaphthalene sodium sulfonate and core-shell structure toughening agent to obtain a component A, wherein no organic solvent is added in the ball milling process, so that the problem of solvent residue is avoided, and the combination is facilitated; in the step of material mixing and oscillation, an ultrasonic oscillator is used for ultrasonic oscillation and stirring, and the ultrasonic wave with specific frequency can promote the impact dispersion of the nano slurry and the component A, so that the proper viscosity and dispersion degree can be conveniently adjusted, and the coating is favorable for brush coating or roller coating construction.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An environment-friendly epoxy resin coating for buildings comprises the following raw materials in parts by weight: 82 parts of modified epoxy resin matrix material, 13 parts of environment-friendly silica gel filler, 12 parts of epoxy active diluent, 10 parts of core-shell structure toughening agent, 6 parts of methylene dinaphthalene sodium sulfonate, and carbon black-SiO24 parts of double nano filler, 5 parts of polydimethylsiloxane and 50 parts of deionized water. Wherein the epoxy active diluent is prepared by mixing ethylene carbonate, propylene carbonate and benzyl alcohol according to the mass ratio of 3:1:1Is prepared by the following steps. The core-shell structure toughening agent is selected from MBS type toughening agents. Carbon black-SiO2The double nano filler is prepared by uniformly mixing carbon black and silica gel with pH of 7 according to the mass ratio of 1:9, precipitating for 24 hours, washing with ethanol, performing vacuum filtration, and performing sterile drying at 55 ℃.
The modified epoxy resin matrix material comprises the following raw materials in parts by weight: 70 parts of bisphenol A type epoxy resin, 15 parts of high-temperature glass flakes, 6 parts of nano zirconia, 2 parts of graphene oxide and 110 parts of dimethyl carbonate; the preparation method of the modified epoxy resin matrix material comprises the following steps:
1) adding bisphenol A epoxy resin and dimethyl carbonate into a high-speed dispersion machine, and heating to 105 ℃ to completely dissolve the bisphenol A epoxy resin;
2) sequentially adding high-temperature glass flakes, nano zirconia and graphene oxide into the system in the step 1), and dispersing and homogenizing at a high speed to form a stable dispersion;
3) introducing the dispersion into a high-pressure homogenizer, homogenizing under 8MPa to obtain a mixed material, placing the mixed material on a hot-pressing mold, hot-pressing at 100 deg.C and 1.2MPa for 80s for molding, cooling to room temperature, solidifying at 150 deg.C for 50min, and pulverizing into matrix material with particle size of 50-100 μm by an ultrafine pulverizer.
The environment-friendly silica gel filler comprises the following raw materials in parts by weight: 125 parts of fluorosilicone raw rubber, 8 parts of hydroxyl silicone oil, 3.6 parts of glass fiber, 1.2 parts of montmorillonite, 0.3 part of nano zinc oxide and 0.16 part of sodium dodecyl sulfate; the specific preparation method of the environment-friendly silica gel filler comprises the following steps:
1) weighing glass fiber, montmorillonite and nano zinc oxide according to the weight parts, sequentially adding the glass fiber, the montmorillonite and the nano zinc oxide into a reaction kettle, and blending at a high speed for 20min to obtain a reinforcing filler mixture;
2) adding the fluorosilicone crude rubber, the hydroxyl silicone oil and the sodium dodecyl sulfate into an internal mixer for internal mixing for 40min to ensure complete fusion to obtain a mixture A;
3) slowly adding the reinforcing filler mixture of 1/3 into the mixture A, heating to 40 ℃, stirring at the rotating speed of 400r/min for 20min, adding the rest reinforcing filler 2/3, heating to 50 ℃, and stirring at 300r/min for 35min to obtain a silica gel mixture;
4) introducing the silica gel mixture into a kneading machine, kneading and molding, feeding into a molding machine, molding at 180 ℃ for 12min, and cooling to normal temperature.
The preparation method of the environment-friendly epoxy resin coating for buildings comprises the following steps:
1) preparing nano slurry: environment-friendly silica gel filler and carbon black-SiO2Adding double nano fillers into a dispersion machine, dropwise adding an epoxy active diluent in the stirring process, dispersing at a high speed for 50min, and then ultrasonically oscillating for 30min to form nano slurry with the fineness of less than 200 nm;
2) preparation of component A: adding the modified epoxy resin matrix material and the sodium methylenedinaphthalene sulfonate into a high-speed dispersion kettle for dispersion for 20min, adding the core-shell structure toughening agent, feeding into a ball mill for dry ball milling for 45min, and filtering under reduced pressure to obtain a component A;
3) mixing and oscillating: under the condition of normal temperature, mixing the nano slurry, the component A, the polydimethylsiloxane and the deionized water, adding the mixture into an ultrasonic oscillator, and carrying out ultrasonic treatment for 8min at the frequency of 40-60KHZ to obtain the environment-friendly epoxy resin coating.
Example 2
An environment-friendly epoxy resin coating for buildings comprises the following raw materials in parts by weight: 77 parts of modified epoxy resin matrix material, 16 parts of environment-friendly silica gel filler, 10 parts of epoxy active diluent, 8 parts of core-shell structure toughening agent, 6 parts of methylene dinaphthalene sodium sulfonate and carbon black-SiO24 parts of double nano filler, 7 parts of polydimethylsiloxane and 49 parts of deionized water. Wherein the epoxy active diluent is prepared by mixing ethylene carbonate, propylene carbonate and benzyl alcohol according to the mass ratio of 3:1: 1. The core-shell structure toughening agent is selected from an ACR type toughening agent. Carbon black-SiO2The double nano filler is prepared by uniformly mixing carbon black and silica gel with pH of 7 according to the mass ratio of 1:10, precipitating for 24 hours, washing with ethanol, performing vacuum filtration, and performing sterile drying at 55 ℃.
The composition and preparation method of the modified epoxy resin matrix material are the same as those of the modified epoxy resin matrix material in example 1.
The composition and preparation method of the environment-friendly silica gel filler are the same as those of the example 1.
The preparation method of the environment-friendly epoxy resin coating for buildings comprises the following steps:
1) preparing nano slurry: environment-friendly silica gel filler and carbon black-SiO2Adding double nano fillers into a dispersion machine, dropwise adding an epoxy active diluent in the stirring process, dispersing at a high speed for 50min, and then ultrasonically oscillating for 30min to form nano slurry with the fineness of less than 200 nm;
2) preparation of component A: adding the modified epoxy resin matrix material and the sodium methylenedinaphthalene sulfonate into a high-speed dispersion kettle for dispersion for 20min, adding the core-shell structure toughening agent, feeding into a ball mill for dry ball milling for 45min, and filtering under reduced pressure to obtain a component A;
3) mixing and oscillating: under the condition of normal temperature, mixing the nano slurry, the component A, the polydimethylsiloxane and the deionized water, adding the mixture into an ultrasonic oscillator, and carrying out ultrasonic treatment for 8min at the frequency of 40-60KHZ to obtain the environment-friendly epoxy resin coating.
Example 3
An environment-friendly epoxy resin coating for buildings comprises the following raw materials in parts by weight: 67 parts of modified epoxy resin matrix material, 15 parts of environment-friendly silica gel filler, 10 parts of epoxy active diluent, 12 parts of core-shell structure toughening agent, 7 parts of methylene dinaphthalene sodium sulfonate, and carbon black-SiO25 parts of double nano filler, 7 parts of polydimethylsiloxane and 38 parts of deionized water. Wherein the epoxy active diluent is prepared by mixing ethylene carbonate, propylene carbonate and benzyl alcohol according to the mass ratio of 3:1: 1. The core-shell structure toughening agent is selected from MBS type toughening agents. Carbon black-SiO2The double nano filler is prepared by uniformly mixing carbon black and silica gel with pH of 7 according to the mass ratio of 1:8.5, precipitating for 24 hours, washing with ethanol, performing vacuum filtration, and performing sterile drying at 55 ℃.
The composition and preparation method of the modified epoxy resin matrix material are the same as those of the modified epoxy resin matrix material in example 1.
The composition and preparation method of the environment-friendly silica gel filler are the same as those of the example 1.
The preparation method of the environment-friendly epoxy resin coating for buildings comprises the following steps:
1) preparing nano slurry: environment-friendly siliconRubber filler and carbon black-SiO2Adding double nano fillers into a dispersion machine, dropwise adding an epoxy active diluent in the stirring process, dispersing at a high speed for 50min, and then ultrasonically oscillating for 30min to form nano slurry with the fineness of less than 200 nm;
2) preparation of component A: adding the modified epoxy resin matrix material and the sodium methylenedinaphthalene sulfonate into a high-speed dispersion kettle for dispersion for 20min, adding the core-shell structure toughening agent, feeding into a ball mill for dry ball milling for 45min, and filtering under reduced pressure to obtain a component A;
3) mixing and oscillating: under the condition of normal temperature, mixing the nano slurry, the component A, the polydimethylsiloxane and the deionized water, adding the mixture into an ultrasonic oscillator, and carrying out ultrasonic treatment for 8min at the frequency of 40-60KHZ to obtain the environment-friendly epoxy resin coating.
Example 4
An environment-friendly epoxy resin coating for buildings comprises the following raw materials in parts by weight: 90 parts of modified epoxy resin matrix material, 18 parts of environment-friendly silica gel filler, 14 parts of epoxy active diluent, 11 parts of core-shell structure toughening agent, 6 parts of methylene dinaphthalene sodium sulfonate, and carbon black-SiO26 parts of double nano filler, 5 parts of polydimethylsiloxane and 56 parts of deionized water. Wherein the epoxy active diluent is prepared by mixing ethylene carbonate, propylene carbonate and benzyl alcohol according to the mass ratio of 3:1: 1. The core-shell structure toughening agent is selected from an ACR type toughening agent. Carbon black-SiO2The double nano filler is prepared by uniformly mixing carbon black and silica gel with pH of 7 according to the mass ratio of 1:10, precipitating for 24 hours, washing with ethanol, performing vacuum filtration, and performing sterile drying at 55 ℃.
The composition and preparation method of the modified epoxy resin matrix material are the same as those of the modified epoxy resin matrix material in example 1.
The composition and preparation method of the environment-friendly silica gel filler are the same as those of the example 1.
The preparation method of the environment-friendly epoxy resin coating for buildings comprises the following steps:
1) preparing nano slurry: environment-friendly silica gel filler and carbon black-SiO2Adding double nano filler into a dispersion machine, dripping epoxy active diluent in the stirring process, dispersing at high speed for 50min, and then ultrasonically oscillating for 30min to form finenessNano slurry less than 200 nm;
2) preparation of component A: adding the modified epoxy resin matrix material and the sodium methylenedinaphthalene sulfonate into a high-speed dispersion kettle for dispersion for 20min, adding the core-shell structure toughening agent, feeding into a ball mill for dry ball milling for 45min, and filtering under reduced pressure to obtain a component A;
3) mixing and oscillating: under the condition of normal temperature, mixing the nano slurry, the component A, the polydimethylsiloxane and the deionized water, adding the mixture into an ultrasonic oscillator, and carrying out ultrasonic treatment for 8min at the frequency of 40-60KHZ to obtain the environment-friendly epoxy resin coating.
Comparative example 1
Compared with the example 1, the comparative example lacks the addition of the environment-friendly silica gel filler, and the specific preparation method comprises the following steps:
1) preparing nano slurry: mixing carbon black-SiO2Adding double nano fillers into a dispersion machine, dropwise adding an epoxy active diluent in the stirring process, dispersing at a high speed for 50min, and then ultrasonically oscillating for 30min to form nano slurry with the fineness of less than 200 nm;
2) preparation of component A: adding the modified epoxy resin matrix material and the sodium methylenedinaphthalene sulfonate into a high-speed dispersion kettle for dispersion for 20min, adding the core-shell structure toughening agent, feeding into a ball mill for dry ball milling for 45min, and filtering under reduced pressure to obtain a component A;
3) mixing and oscillating: under the condition of normal temperature, mixing the nano slurry, the component A, the polydimethylsiloxane and the deionized water, adding the mixture into an ultrasonic oscillator, and carrying out ultrasonic treatment for 8min at the frequency of 40-60KHZ to obtain the environment-friendly epoxy resin coating.
Comparative example 2
Compared with example 1, the comparative example lacks modification of epoxy resin, and comprises the following raw materials in parts by weight: 82 parts of bisphenol A type epoxy resin, 13 parts of environment-friendly silica gel filler, 12 parts of epoxy active diluent, 10 parts of core-shell structure toughening agent, 6 parts of methylene dinaphthalene sodium sulfonate and carbon black-SiO24 parts of double nano filler, 5 parts of polydimethylsiloxane and 50 parts of deionized water. Wherein the epoxy active diluent is prepared by mixing ethylene carbonate, propylene carbonate and benzyl alcohol according to the mass ratio of 3:1: 1. The core-shell structure toughening agent is selected from MBS typeA toughening agent. Carbon black-SiO2The double nano filler is prepared by uniformly mixing carbon black and silica gel with pH of 7 according to the mass ratio of 1:9, precipitating for 24 hours, washing with ethanol, performing vacuum filtration, and performing sterile drying at 55 ℃.
The preparation method of this comparative example comprises the following steps:
1) preparing nano slurry: environment-friendly silica gel filler and carbon black-SiO2Adding double nano fillers into a dispersion machine, dropwise adding an epoxy active diluent in the stirring process, dispersing at a high speed for 50min, and then ultrasonically oscillating for 30min to form nano slurry with the fineness of less than 200 nm;
2) preparation of component A: adding bisphenol A epoxy resin and methylene dinaphthalene sodium sulfonate into a high-speed dispersion kettle for dispersing for 20min, adding a core-shell structure toughening agent, sending into a ball mill for dry ball milling for 45min, and filtering under reduced pressure to obtain a component A;
3) mixing and oscillating: under the condition of normal temperature, mixing the nano slurry, the component A, the polydimethylsiloxane and the deionized water, adding the mixture into an ultrasonic oscillator, and carrying out ultrasonic treatment for 8min at the frequency of 40-60KHZ to obtain the environment-friendly epoxy resin coating.
Comparative example 3
Refer to the waterborne epoxy coating prepared in example 1 of patent publication No. CN 104910759A.
Performance testing
For the epoxy resin coatings prepared in examples 1-4 and comparative examples 1-3, the content of Volatile Organic Compounds (VOC) is tested by referring to GB/T18582-2008, the wear resistance is tested by referring to GB/T1768-2006, the impact resistance is tested by referring to GB/T1732-1993, the salt spray resistance is tested by referring to GB/T1771-1991, the aging resistance is tested by referring to a conventional method, and the specific detection results are shown in Table 1.
TABLE 1 epoxy resin coating Performance test
Figure BDA0001783437400000131
As can be seen from the above table, compared with the comparative example, the environment-friendly epoxy resin coating prepared by the embodiment of the invention has low content of volatile organic compounds, and has better wear resistance, impact resistance, salt spray resistance and aging resistance. Comparative example 1 lacks the environmental silica gel filler, causes the compatibility of other fillers and modified epoxy resin matrix material to be worsened, lacks the improvement of modified epoxy resin elasticity and strength, is easy to crack and age, causes the abrasion resistance, impact resistance and aging resistance to be obviously reduced. In the comparative example 2, due to the lack of modification of epoxy resin, the improvement of the performances of wear resistance, heat resistance, impact toughness and the like of the high-temperature glass flake, the nano-zirconia and the graphene oxide is obviously reduced.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims (5)

1. The environment-friendly epoxy resin coating for buildings is characterized by comprising the following raw materials in parts by weight: 60-90 parts of modified epoxy resin matrix material, 12-18 parts of environment-friendly silica gel filler, 6-15 parts of epoxy active diluent, 8-13 parts of core-shell structure toughening agent, 4-8 parts of sodium methylene dinaphthalenesulfonate and carbon black-SiO22-6 parts of double nano-filler, 3-8 parts of polydimethylsiloxane and 32-58 parts of deionized water;
the modified epoxy resin matrix material comprises the following raw materials in parts by weight: 70 parts of bisphenol A type epoxy resin, 15 parts of high-temperature glass flakes, 6 parts of nano zirconia, 2 parts of graphene oxide and 110 parts of dimethyl carbonate; the preparation method of the modified epoxy resin matrix material comprises the following steps:
1) adding bisphenol A epoxy resin and dimethyl carbonate into a high-speed dispersion machine, and heating to 105 ℃ to completely dissolve the bisphenol A epoxy resin;
2) sequentially adding high-temperature glass flakes, nano zirconia and graphene oxide into the system in the step 1), and dispersing and homogenizing at a high speed to form a stable dispersion;
3) introducing the dispersion into a high-pressure homogenizer, homogenizing under 8MPa to obtain a mixed material, placing the mixed material on a hot-pressing mold, hot-pressing at 100 deg.C and 1.2MPa for 80s for molding, cooling to room temperature, curing at 150 deg.C for 50min, and pulverizing into matrix material with particle size of 50-100 μm by an ultrafine pulverizer;
the environment-friendly silica gel filler comprises the following raw materials in parts by weight: 125 parts of fluorosilicone raw rubber, 8 parts of hydroxyl silicone oil, 3.6 parts of glass fiber, 1.2 parts of montmorillonite, 0.3 part of nano zinc oxide and 0.16 part of sodium dodecyl sulfate; the specific preparation method of the environment-friendly silica gel filler comprises the following steps:
1) weighing glass fiber, montmorillonite and nano zinc oxide according to the weight parts, sequentially adding the glass fiber, the montmorillonite and the nano zinc oxide into a reaction kettle, and blending at a high speed for 20min to obtain a reinforcing filler mixture;
2) adding the fluorosilicone crude rubber, the hydroxyl silicone oil and the sodium dodecyl sulfate into an internal mixer for internal mixing for 40min to ensure complete fusion to obtain a mixture A;
3) slowly adding the reinforcing filler mixture of 1/3 into the mixture A, heating to 40 ℃, stirring at the rotating speed of 400r/min for 20min, adding the rest reinforcing filler 2/3, heating to 50 ℃, and stirring at 300r/min for 35min to obtain a silica gel mixture;
4) introducing the silica gel mixture into a kneading machine, kneading and molding, feeding into a molding machine, molding at 180 ℃ for 12min, and cooling to normal temperature.
2. The environment-friendly epoxy resin paint for buildings as claimed in claim 1, wherein the epoxy reactive diluent is prepared by mixing ethylene carbonate, propylene carbonate and benzyl alcohol according to a mass ratio of 3:1: 1.
3. The architectural environment-friendly epoxy resin coating as claimed in claim 1, wherein the core-shell structure toughening agent is selected from an MBS type toughening agent or an ACR type toughening agent.
4. The architectural environment-friendly epoxy resin coating according to claim 1, wherein the carbon black-SiO2The double nano filler is prepared by uniformly mixing carbon black and silica gel with pH of 7 according to the mass ratio of 1:8-10, precipitating for 24h, washing with ethanol, performing vacuum filtration, and performing sterile drying at 55 ℃.
5. The architectural environment-friendly epoxy resin paint as claimed in claim 1, wherein the preparation method of the architectural environment-friendly epoxy resin paint comprises the following steps:
1) preparing nano slurry: environment-friendly silica gel filler and carbon black-SiO2Adding double nano fillers into a dispersion machine, dropwise adding an epoxy active diluent in the stirring process, dispersing at a high speed for 50min, and then ultrasonically oscillating for 30min to form nano slurry with the fineness of less than 200 nm;
2) preparation of component A: adding the modified epoxy resin matrix material and the sodium methylenedinaphthalene sulfonate into a high-speed dispersion kettle for dispersion for 20min, adding the core-shell structure toughening agent, feeding into a ball mill for dry ball milling for 45min, and filtering under reduced pressure to obtain a component A;
3) mixing and oscillating: under the condition of normal temperature, mixing the nano slurry, the component A, the polydimethylsiloxane and the deionized water, adding the mixture into an ultrasonic oscillator, and carrying out ultrasonic treatment for 8min at the frequency of 40-60KHZ to obtain the environment-friendly epoxy resin coating.
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