CN111875320B - Super-hydrophobic microcapsule polymer cement-based anticorrosive paint and preparation method and application thereof - Google Patents

Super-hydrophobic microcapsule polymer cement-based anticorrosive paint and preparation method and application thereof Download PDF

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CN111875320B
CN111875320B CN202010834945.9A CN202010834945A CN111875320B CN 111875320 B CN111875320 B CN 111875320B CN 202010834945 A CN202010834945 A CN 202010834945A CN 111875320 B CN111875320 B CN 111875320B
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weight
hydrophobic
stirring
graphene oxide
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CN111875320A (en
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赵丕琪
刘乐乐
芦令超
王晓伟
侯鹏坤
张丽娜
程新
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/02—Treatment
    • C04B20/023—Chemical treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1066—Oxides, Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C04B2111/00508—Cement paints
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2092—Resistance against biological degradation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

The invention relates to the field of cement anticorrosive coatings, in particular to a super-hydrophobic microcapsule polymer cement-based anticorrosive coating and a preparation method and application thereof. The coating comprises the following raw materials in parts by weight: 65-85 parts of cement, 65-70 parts of quartz sand, 0.5-1.0 part of reinforcing agent, 0.17-0.32 part of retarder, 45-55 parts of emulsion, 15-18 parts of water, 1.1-1.8 parts of film-forming additive, 0.47-1.4 parts of light stabilizer, 0.2-0.6 part of preservative, 0.05-0.3 part of hydrophobically modified graphene oxide and 6-8 parts of aqueous microcapsule emulsion, wherein the aqueous microcapsule emulsion takes a hydrophobic material as a core and takes SiO2The gel is a core-shell structure formed by a shell layer. The anticorrosive paint avoids adverse effects on a cement hydration hardening process and a polymer film forming process, and effectively solves the problem of compatibility of a hydrophobing agent with emulsion and cement.

Description

Super-hydrophobic microcapsule polymer cement-based anticorrosive paint and preparation method and application thereof
Technical Field
The invention relates to the field of cement anticorrosive coatings, in particular to a super-hydrophobic microcapsule polymer cement-based anticorrosive coating and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The polymer cement waterproof coating is a two-component water-based waterproof coating which is prepared by taking polymer emulsion such as acrylic ester, ethylene-vinyl acetate and the like and cement as main raw materials, adding a filler and other auxiliary agents, and then carrying out water volatilization and cement hydration reaction to solidify into a film. The waterproof coating overcomes the defects of inadaptation and deformation, easy cracking, poor ion erosion resistance, insufficient durability of organic coatings and poor compatibility of base surfaces of the traditional inorganic coatings, has the characteristics of high flexibility, waterproofness and inorganic material strength of polymer coatings, capability of being directly constructed on a wet base layer, easiness in bonding with the base surfaces and the like, and is widely applied to waterproof construction in the fields of toilets, bathrooms, kitchens, building outer walls, ocean engineering, underground engineering and the like.
Although the polymer cement waterproof coating is widely applied, the inorganic part of the polymer cement waterproof coating is mostly hydrophilic substances, and the polymer emulsion also contains a large amount of hydrophilic surfactants, carboxyl and other hydrophilic groups, so that the coating is easily infiltrated by water in the service process, and the waterproof and anti-permeability performance is insufficient.
The super-hydrophobic material is a material with a surface contact angle with water larger than 150 degrees and a rolling angle smaller than 10 degrees, and has excellent waterproof and anti-corrosion properties. By endowing the polymer cement-based waterproof coating with super-hydrophobic performance, the wetting property of water on the surface of the coating can be fundamentally prevented, the invasion of water is prevented, and the service life of the coating is prolonged.
Currently, there are two main ways to construct coatings that are superhydrophobic. Firstly, the super-hydrophobic property is endowed to the surface of the coating by constructing a micro-nano structure with low surface energy. The second is to construct an internal hydrophobic structure by internally doping a hydrophobic agent. However, the superhydrophobic surface constructed in the first way has poor stability and easily loses superhydrophobic performance after being subjected to external mechanical stress. In the second mode, the hydrophobic component is difficult to uniformly disperse, and more importantly, the introduction of the hydrophobic agent seriously affects the physicochemical reaction between related hydrophilic groups in the hydration and hardening process of the cement and the film forming process of the polymer, so that the coating has loose and porous structure, the mechanical property is reduced, and the integral service performance is deteriorated.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the super-hydrophobic microcapsule polymer cement-based anticorrosive coating, and the preparation method and the application thereof, the anticorrosive coating avoids the adverse effects on the cement hydration hardening process and the polymer film forming process after the hydrophobic material is added, and effectively solves the problem of the compatibility of the hydrophobic agent with the emulsion and the cement. In order to achieve the above object, the technical solution of the present invention is specifically as follows:
in a first aspect of the invention, a super-hydrophobic microcapsule polymer cement-based anticorrosive coating is provided, which comprises the following raw materials in parts by weight: 65-85 parts of cement, 65-70 parts of quartz sand, 0.5-1.0 part of reinforcing agent, 0.17-0.32 part of retarder, 45-55 parts of emulsion, 15-18 parts of water, 1.1-1.8 parts of film-forming additive, 0.47-1.4 parts of light stabilizer, 0.2-0.6 part of preservative, 0.05-0.3 part of hydrophobically modified graphene oxide and 6-8 parts of aqueous microcapsule emulsion, wherein the aqueous microcapsule emulsion takes a hydrophobic material as a core and takes SiO2The gel is a core-shell structure formed by a shell layer.
Further, the paint also comprises 20-25 parts of filler, optionally, the filler comprises any one or more of calcium carbonate powder, mica powder, silica powder, talcum powder and the like, and the filler is helpful for improving the mechanical property and the dimensional stability of the paint.
Further, the cement includes any one of portland cement, sulphoaluminate cement, and the like.
Further, the reinforcing agent is fiber, and comprises one or more of polypropylene fiber, steel fiber, carbon fiber and the like, and the addition of the fiber is helpful for increasing the crack resistance and impact resistance of the coating and improving the mechanical property.
Further, the retarder comprises one or more of tartaric acid, citric acid, boric acid and the like, and the main functions of the retarder comprise prolonging the hydration hardening time of cement and delaying Ca2+To prevent the emulsion from being over hydratedDemulsification occurs in the process.
Further, the emulsion comprises one or more of polyacrylate emulsion, ethylene-vinyl acetate copolymer emulsion, neoprene emulsion and the like, is a main film forming substance of the polymer cement waterproof coating, and provides excellent flexibility and waterproof performance.
Further, the light stabilizer comprises one or a mixture of more of benzophenones, benzotriazole, hindered amine and the like, and can remarkably increase the ultraviolet aging resistance of the coating.
Further, the preservative comprises one or a mixture of more of sodium pentachlorophenate, TPN (2,4,5, 6-tetrachloroisophthalonitrile), TBZ (2- (4-thiazolyl) benzimidazole) and the like, and the preservative mainly has the effects of preventing mildew, sterilizing and inhibiting the growth and reproduction of microorganisms on the surface.
Further, the hydrophobically modified graphene oxide is a fluorosilane hydrophobic agent modified graphene oxide. According to the invention, the fluorine-containing silane hydrophobic agent is used for modifying graphene oxide, after the graphene oxide is doped into the coating, the sheet structure characteristic of the graphene oxide is utilized to cut off capillary channels inside the coating, and the inside is blocked into irregular units to form a micro-space structure, so that the coating has the functions of freezing resistance, water resistance, crack resistance and the like. In addition, the addition of the graphene oxide prolongs the transmission path of water in the material, greatly delays the corrosion of the coating and increases the protection effect on the matrix.
Further, in the aqueous microcapsule emulsion, the hydrophobic material comprises any one or a mixture of several of dimethyl silicone oil and polymethylhydrosiloxane. SiO 22The coated hydrophobic material is slowly released after the coating forms a film, so that adverse effects on the cement hydration hardening process and the polymer film forming process are avoided. In addition, the microcapsule emulsion has water-based property, so that the problem of compatibility of the water repellent agent with the emulsion and cement is effectively solved.
Further, the super-hydrophobic microcapsule polymer cement-based anticorrosive coating also comprises 0.5-0.8 part by weight of an antifoaming agent, and optionally, the antifoaming agent comprises any one or more of an organic silicon antifoaming agent, a mineral oil antifoaming agent and the like.
In a second aspect of the present invention, there is provided a method for preparing the superhydrophobic microcapsule polymer cement-based anticorrosive coating, comprising the steps of:
preparing hydrophobic modified graphene oxide:
(1) and mixing the graphene oxide and the volatile solvent, and then carrying out ultrasonic dispersion to obtain a graphene oxide dispersion liquid for later use.
(2) And adding fluorosilane into the graphene oxide dispersion liquid, stirring while reacting under a heating condition, and washing, drying and grinding the obtained product in sequence after the reaction is finished to obtain the hydrophobically modified graphene oxide for later use.
Preparation of aqueous microcapsule emulsion:
(3) mixing water and polyvinyl alcohol, stirring the mixture under the condition of constant temperature and heat preservation until the mixture is clear and has no visible particles, and then adjusting the mixture to be alkaline by using ammonia water to obtain a polyvinyl alcohol solution for later use.
(4) Hydrophilic nano SiO2Mixing aerogel and volatile solvent, performing ultrasonic dispersion, adding a hydrophobic modifier with one hydrophilic end and one lipophilic end and water, stirring and reacting under the condition of constant temperature and heat preservation, separating out a solid product after the reaction is finished, drying and grinding the solid product to obtain modified nano SiO2And then standby.
(5) Hydrophobic agent, Tetraethoxysilane (TEOS) and the modified nano SiO obtained in the step (4)2And (4) uniformly mixing, adding the polyvinyl alcohol solution obtained in the step (3) and a defoaming agent, and then shearing and emulsifying to obtain the water-based microcapsule emulsion.
Preparation of polymer cement waterproof coating:
(6) and (3) uniformly mixing cement, calcium carbonate, quartz sand, a reinforcing agent, a retarder and the hydrophobic modified graphene oxide prepared in the step (2) to obtain a first mixture for later use.
(7) And (3) uniformly mixing the emulsion, water, the film-forming auxiliary agent, the aqueous microcapsule emulsion prepared in the step (5), the light stabilizer and the preservative to obtain a second mixture for later use.
(8) And adding the first mixture into the second mixture in batches, uniformly stirring, adding the defoaming agent, and uniformly stirring to obtain the super-hydrophobic microcapsule polymer cement-based anticorrosive coating.
In step (1), the volatile solvent includes at least one of any suitable organic solvent such as absolute ethanol. The addition amount of the volatile solvent is enough to disperse the graphene oxide, and a person skilled in the art can select the addition amount of the absolute ethyl alcohol according to the actual dosage of the graphene oxide, and the invention is not particularly limited.
In the step (1), the ultrasonic dispersion time can be selected to be 1-2h, graphene oxide is uniformly dispersed in a volatile solvent through ultrasonic dispersion, agglomeration is avoided, the graphene oxide is conveniently and uniformly dispersed in the raw material in the follow-up process, and capillary channels in the coating are cut and blocked by utilizing the characteristic of the flaky structure of the graphene oxide.
In the step (2), the fluorosilane is added in a proportion of 3-5 parts by weight of graphene oxide and 4.5-7.5 parts by weight of fluorine-containing silane. When the graphene oxide is taken in the above weight parts, the dispersion may be performed by using 150ml or more of absolute ethyl alcohol. In the invention, fluorine-containing groups with extremely low surface energy can be grafted on the surface of graphene oxide by utilizing fluorosilane modification, and the graphene oxide can prevent water from permeating when being doped into the polymer cement waterproof coating.
In the step (2), the heating temperature is 60-80 ℃, the reaction time is 20-24h, the stirring speed is 5000-.
In the step (2), the washing mode is vacuum filtration washing for 2-3 times, and the drying mode is vacuum drying for 8-12h at 50-60 ℃.
In the step (3), the adding proportion of the water and the polyvinyl alcohol is 20-30 parts by weight in sequence: 1-2 parts by weight.
In the step (3), the temperature of constant temperature heat preservation is 50-80 ℃, and the pH value of alkalinity is 8-9. In the invention, after the TEOS coated in the microcapsule permeates to the outside, the hydrolysis condensation reaction can be carried out under the alkaline condition, thereby further enhancing the SiO2Shell layerStability and mechanical properties of the composition.
In the step (4), the volatile solvent comprises any suitable organic solvent in absolute ethyl alcohol and the like, and the addition amount of the volatile solvent is enough to disperse the hydrophilic nano SiO2And (4) aerogel.
In the step (4), the hydrophilic nano SiO2The addition proportions of the aerogel, the hydrophobic modifier and the water are 5-10 parts by weight in sequence: 0.1-2 parts by weight: 3-5 parts by weight. Taking the hydrophilic nano SiO in parts by weight2In the case of aerogel, 100-150ml of anhydrous ethanol can be used for dispersion.
Preferably, in the step (4), the modifier is one or a mixture of more of hexamethyldisilazane, gamma-methacryloxypropyl, stearic acid, trichloromethylsilane, octadecyltriethoxysilane, octadecyltrichlorosilane, etc., and the modifier is effective on SiO2The hydrophilic groups of the surface are modified to some extent.
In the step (4), the ultrasonic dispersion time is 3-5min, the constant temperature heat preservation time is 40-60 ℃, the stirring speed is 2000-4000r/min, the reaction time is 12-24h, and the method for separating the solid product is preferably filtration, and has the characteristic of convenient operation.
In the step (5), the hydrophobic agent, ethyl orthosilicate and modified nano SiO2The addition proportions of the polyvinyl alcohol and the defoaming agent in the polyvinyl alcohol solution are as follows: 8-15 parts, 3-5 parts, 0.5-1.5 parts, 1-2 parts and 0.3-0.5 part.
In the step (5), the shearing and emulsifying rotating speed is 8000-15000r/min, and the time is 5-15 min.
In the step (5), the hydrophobic agent is preferably any one or a mixture of several of dimethyl silicone oil and polymethylhydrosiloxane, and the hydrophobic agent does not react with TEOS, so that the stability of the hydrophobic agent in the microcapsule is ensured.
In the step (6), the uniform mixing is performed in a manner of mixing at 500r/min for 20-30min at 400-.
In the step (7), the uniformly mixing mode is as follows: mixing at low speed (57-67r/min) for 3-4min, and then mixing at high speed (115-135r/min) for 5-10 min.
In the step (8), the stirring uniformly mode is as follows: adding the first mixture into the second mixture for 2-3 times, stirring at low speed (57-67r/min) for 2-3min, stirring at high speed (115-135r/min) for 5-10min, adding defoaming agent, and stirring at low speed (57-67r/min) for 3-5 min.
In the steps (5) and (8), the defoaming agent comprises any one or more of an organic silicon defoaming agent, a mineral oil defoaming agent and the like.
It should be noted that there is no specific order in the preparation of the hydrophobic modified graphene oxide and the preparation of the aqueous microcapsule emulsion in the above preparation method, that is, the hydrophobic modified graphene oxide may be prepared first and then the aqueous microcapsule emulsion is prepared, or the aqueous microcapsule emulsion may be prepared first and then the hydrophobic modified graphene oxide is prepared.
Based on this, the above-mentioned sequence between steps (1) - (2) and (3) - (5) is only for convenience of description, and does not constitute a specific sequence, that is, steps (3) - (5) may be performed first and then steps (1) - (2) may be performed, or steps (1) - (2) may be performed first and then steps (3) - (5) may be performed.
Similarly, no specific order of arrangement is defined between the above steps (3) and (4), and no specific order of arrangement is defined between the steps (6) and (7).
In a third aspect of the invention, the application of the super-hydrophobic microcapsule polymer cement-based anticorrosive paint in the fields of bathrooms, kitchens, building exterior walls, ocean engineering, underground engineering and the like is disclosed.
Compared with the prior art, the invention has the following beneficial effects:
(1) the existing polymer cement waterproof coatings are insufficient in waterproof and anti-permeability performance, particularly in a high-humidity environment, a coating is easy to absorb water and swell, water and salt transmission is difficult to effectively retard, and the protective performance of the coating based on a concrete body is insufficient. The invention endows the polymer cement coating with super-hydrophobic performance, fundamentally prevents water from infiltrating on the surface of the coating, and improves the waterproof and anti-permeability performance of the polymer cement coating.
(2) The existing coatings realize super-hydrophobic performance by constructing a micro-nano structure on the surface of the coatings, and the method has the defect of poor hydrophobic stability. According to the invention, the water-based microcapsule is doped on the basis of doping the flaky graphene oxide, namely, on the basis of blocking the coating into a micro space by a flaky material, the microcapsule is utilized to modify the interior of the micro space to form a three-dimensional multiple waterproof structure; therefore, by constructing a three-dimensional hydrophobic network in the coating, the overall hydrophobicity of the polymer cement is realized, and the polymer cement is not limited to the super-hydrophobic property of the coating surface.
(3) The existing coatings are internally doped with hydrophobic agents to improve the performances of water resistance, impermeability and the like, the mode often has the defect that hydrophobic components are difficult to uniformly disperse, and more importantly, the introduction of the hydrophobic agents seriously affects the physical and chemical reactions among related hydrophilic groups in the cement hydration hardening process and the polymer film forming process, so that the coating structure is loose and porous, the mechanical property is reduced, and the integral service performance is deteriorated. The invention prepares SiO by taking hydrophobic material as a core2Mixing the water-thinned microcapsule emulsion with gel as shell and SiO in the waterproof polymer cement coating2The hydrophobic agent coated by the gel shell layer is slowly released after the coating is formed into a film, so that adverse effects on a polymer film forming process and a cement hydration process are avoided.
(4) The microcapsule emulsion is water-based, and effectively solves the problem of compatibility of a hydrophobic agent with emulsion and cement. The hydrophobic component and the hydrophilic material are difficult to be uniformly fused together, and the water-based microcapsule emulsion is prepared and uniformly mixed with the water-based emulsion to be further applied to the polymer cement waterproof coating, so that the hydrophobic component can be uniformly dispersed in the whole system, and the hydrophobic modification of the whole structure is realized.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a diagram showing the effect of the emulsification process of the aqueous microcapsule emulsion in the embodiment of the present invention.
FIG. 2 is a water repellency test result chart of an anticorrosive coating prepared according to a first embodiment of the present invention.
Fig. 3 is a schematic of an aqueous microcapsule emulsion prepared in an example of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
First embodiment
The preparation method of the super-hydrophobic microcapsule polymer cement-based anticorrosive paint comprises the following steps:
1. preparing hydrophobic modified graphene oxide:
1.1 adding 5 parts by weight of graphene oxide into 150ml of absolute ethyl alcohol, and then carrying out ultrasonic dispersion for 2 hours to obtain a graphene oxide dispersion liquid.
1.2 adding 7 parts by weight of polyperfluoroalkyl siloxane into the graphene oxide dispersion liquid, adjusting the reaction temperature to 65 ℃ for reaction for 24 hours, and violently stirring at the speed of 8000r/min in the reaction process. And after the reaction is finished, carrying out vacuum filtration on the reaction solution, washing the solid product for 3 times, then carrying out vacuum drying at 50 ℃ for 12 hours, and grinding to obtain the hydrophobic modified graphene oxide for later use.
2. Preparation of aqueous microcapsule emulsion:
2.1 mixing 23 parts by weight of deionized water with 1.6 parts by weight of polyvinyl alcohol, stirring at a constant temperature of 70 ℃ until the solution is clear and has no visible particles, and adjusting the pH to 8 by using ammonia water to obtain the polyvinyl alcohol solution for later use.
2.2 mixing 8 parts by weight of hydrophilic nano SiO2Adding aerogel into 120ml of absolute ethyl alcohol, performing ultrasonic dispersion for 5min, then adding 1.5 parts by weight of hexamethyldisilazane and 5 parts by weight of deionized water, reacting for 20h at a constant temperature of 40 ℃, stirring at a speed of 2000r/min in the reaction process, filtering a solid product after the reaction is finished, drying and grinding into powder to obtain the modified nano SiO2And then standby.
2.3 mixing 10 weight parts of dimethyl silicone oil, 5 weight parts of TEOS, 1.2 weight parts of modified nano SiO prepared in step 2.22Adding into a stirrer, mixing at 700r/min, adding the polyvinyl alcohol solution prepared in step 2.1 and 0.5 weight part of silicone defoamer, and shearing and emulsifying at 5000r/min for 8min with an emulsifying machine to obtain water-based microcapsule emulsion (refer to fig. 1).
3. Preparation of polymer cement waterproof coating:
3.1 placing 70 parts by weight of Portland cement, 22 parts by weight of calcium carbonate powder, 65 parts by weight of fine quartz sand, 0.6 part by weight of steel fiber, 0.2 part by weight of tartaric acid and 0.2 part by weight of the hydrophobically modified graphene oxide prepared in the step 1.2 of the embodiment in a stirrer, and mixing at the speed of 500r/min for 20min to obtain powder.
3.2 placing 50 parts by weight of emulsion, 17 parts by weight of deionized water, 1.1 parts by weight of film-forming auxiliary agent, 6 parts by weight of the aqueous microcapsule emulsion prepared in the step 2.3 of the embodiment, 0.5 part by weight of benzotriazole light stabilizer and 0.3 part by weight of preservative into a cement paste mixer, stirring at a low speed (60r/min) for 4min, and then stirring at a high speed (120r/min) for 8min to obtain a liquid material.
3.3, evenly adding the powder prepared in the step 3.1 into the liquid material prepared in the step 3.2 for 3 times, then stirring at a low speed (60r/min) for 2min, then stirring at a high speed (120r/min) for 10min, adding 0.8 part by weight of an organic silicon defoaming agent after completion, and stirring at a low speed (60r/min) for 5min to obtain the super-hydrophobic microcapsule polymer cement-based anticorrosive coating.
Second embodiment
The preparation method of the super-hydrophobic microcapsule polymer cement-based anticorrosive paint comprises the following steps:
1. preparing hydrophobic modified graphene oxide:
1.1 adding 4.5 parts by weight of graphene oxide into 160ml of absolute ethyl alcohol, and then carrying out ultrasonic dispersion for 1 hour to obtain a graphene oxide dispersion liquid.
1.2 adding 7.5 parts by weight of tridecafluorooctyltriethoxysilane into the graphene oxide dispersion liquid, adjusting the reaction temperature to 60 ℃ for 24 hours, and violently stirring at the speed of 6000r/min in the reaction process. And after the reaction is finished, carrying out vacuum filtration on the reaction solution, washing the solid product for 3 times, then carrying out vacuum drying at 60 ℃ for 8 hours, and grinding to obtain the hydrophobic modified graphene oxide for later use.
2. Preparation of aqueous microcapsule emulsion:
2.1 mixing 20 parts by weight of deionized water with 1.3 parts by weight of polyvinyl alcohol, stirring at a constant temperature of 50 ℃ until the solution is clear and has no visible particles, and adjusting the pH to 9 by using ammonia water to obtain the polyvinyl alcohol solution for later use.
2.2 mixing 5 parts by weight of hydrophilic nano SiO2Adding aerogel into 100ml of absolute ethyl alcohol, performing ultrasonic dispersion for 3min, adding 0.5 part by weight of stearic acid and 3 parts by weight of deionized water, reacting at the constant temperature of 55 ℃ for 12h, stirring at the speed of 4000r/min in the reaction process, filtering out a solid product after the reaction is finished, drying and grinding into powder to obtain the modified nano SiO2And then standby.
2.3 adding 8 weight parts of polymethylhydrosiloxane, 3 weight parts of TEOS and 0.5 weight part of modified nano SiO prepared in the step 2.22Adding into a stirrer, mixing at 700r/min, adding the polyvinyl alcohol solution prepared in step 2.1 and 0.3 weight part of mineral oil defoaming agent, and shearing and emulsifying at 15000r/min with an emulsifying machine for 8min to obtain water-based microcapsule emulsion(refer to fig. 1), ready for use.
3. Preparation of polymer cement waterproof coating:
3.1 placing 65 parts by weight of Portland cement, 25 parts by weight of calcium carbonate powder, 68 parts by weight of fine quartz sand, 0.5 part by weight of propylene fiber, 0.17 part by weight of boric acid and 0.25 part by weight of the hydrophobically modified graphene oxide prepared in the step 1.2 of the embodiment in a stirrer, and mixing at the speed of 400r/min for 25min to obtain powder.
3.2 placing 45 parts by weight of emulsion, 16 parts by weight of deionized water, 1.5 parts by weight of film-forming assistant, 8 parts by weight of the aqueous microcapsule emulsion prepared in the step 2.3 of the embodiment, 0.47 part by weight of benzophenone light stabilizer and 0.5 part by weight of preservative into a cement paste mixer, stirring at a low speed (57r/min) for 3min, and then stirring at a high speed (115r/min) for 10min to obtain a liquid material.
3.3, evenly adding the powder prepared in the step 3.1 into the liquid material prepared in the step 3.2 for 2 times, then stirring at a low speed (57r/min) for 3min, then stirring at a high speed (115r/min) for 7min, adding 0.6 part by weight of mineral oil defoaming agent after the stirring is finished, and stirring at a low speed (57r/min) for 5min to obtain the super-hydrophobic microcapsule polymer cement-based anticorrosive coating.
Third embodiment
The preparation method of the super-hydrophobic microcapsule polymer cement-based anticorrosive paint comprises the following steps:
1. preparing hydrophobic modified graphene oxide:
1.1 adding 3.5 parts by weight of graphene oxide into 150ml of absolute ethyl alcohol, and then carrying out ultrasonic dispersion for 1 hour to obtain a graphene oxide dispersion liquid.
1.2 adding 4.5 parts by weight of tridecafluorooctyltrimethoxysilane into the graphene oxide dispersion liquid, adjusting the reaction temperature to 60 ℃ for 20 hours, and violently stirring at the speed of 5000r/min in the reaction process. And after the reaction is finished, carrying out vacuum filtration on the reaction solution, washing the solid product for 2 times, then carrying out vacuum drying at 50 ℃ for 8.5h, and grinding to obtain the hydrophobic modified graphene oxide for later use.
2. Preparation of aqueous microcapsule emulsion:
2.1 mixing 30 parts by weight of deionized water with 2 parts by weight of polyvinyl alcohol, then stirring at a constant temperature of 70 ℃ until the solution is clear and has no macroscopic particles, and adjusting the pH to 9 by using ammonia water to obtain a polyvinyl alcohol solution for later use.
2.2 mixing 8 parts by weight of hydrophilic nano SiO2Adding aerogel into 150ml of absolute ethyl alcohol, performing ultrasonic dispersion for 5min, then adding 2 parts by weight of octadecyl triethoxysilane and 4 parts by weight of deionized water, reacting for 20h at a constant temperature of 55 ℃, stirring at a speed of 4000r/min in the reaction process, filtering a solid product after the reaction is finished, drying and grinding into powder to obtain the modified nano SiO2And then standby.
2.3 mixing 12 weight parts of dimethyl silicone oil, 4 weight parts of TEOS, 1.5 weight parts of modified nano SiO prepared in step 2.22Adding into a stirrer, mixing at 500r/min, adding the polyvinyl alcohol solution prepared in step 2.1 and 0.35 weight part of mineral oil defoaming agent, and shearing and emulsifying at 8000r/min for 5min with an emulsifying machine to obtain water-based microcapsule emulsion (refer to figure 1).
3. Preparation of polymer cement waterproof coating:
3.1 placing 75 parts by weight of Portland cement, 20 parts by weight of silicon dioxide powder, 70 parts by weight of fine quartz sand, 0.8 part by weight of carbon fiber, 0.3 part by weight of citric acid and 0.3 part by weight of the hydrophobically modified graphene oxide prepared in the step 1.2 of the embodiment in a stirrer, and mixing at the speed of 500r/min for 30min to obtain powder.
3.2 placing 50 parts by weight of emulsion, 15 parts by weight of deionized water, 1.6 parts by weight of film-forming assistant, 7.5 parts by weight of the aqueous microcapsule emulsion prepared in the step 2.3 of the embodiment, 1.2 parts by weight of hindered amine light stabilizer and 0.2 part by weight of preservative into a cement paste mixer, stirring at a low speed (65r/min) for 4min, and then stirring at a high speed (135r/min) for 5min to obtain a liquid material.
3.3, evenly adding the powder prepared in the step 3.1 into the liquid material prepared in the step 3.2 for 3 times, then stirring for 3min at a low speed (65r/min), then stirring for 5min at a high speed (130r/min), adding 0.8 part by weight of mineral oil defoaming agent after completion, and stirring for 5min at a low speed (65r/min) to obtain the super-hydrophobic microcapsule polymer cement-based anticorrosive coating.
Fourth embodiment
The preparation method of the super-hydrophobic microcapsule polymer cement-based anticorrosive paint comprises the following steps:
1. preparing hydrophobic modified graphene oxide:
1.1 adding 3 parts by weight of graphene oxide into 150ml of absolute ethyl alcohol, and then carrying out ultrasonic dispersion for 1 hour to obtain a graphene oxide dispersion liquid.
1.2 adding 6.5 parts by weight of heptadecafluorodecyltriethoxysilane into the graphene oxide dispersion liquid, adjusting the reaction temperature to 80 ℃ for 21 hours, and violently stirring at the speed of 7000r/min in the reaction process. And after the reaction is finished, carrying out vacuum filtration on the reaction solution, washing the solid product for 3 times, then carrying out vacuum drying at 50 ℃ for 8 hours, and grinding to obtain the hydrophobic modified graphene oxide for later use.
2. Preparation of aqueous microcapsule emulsion:
2.1 mixing 20 parts by weight of deionized water and 1 part by weight of polyvinyl alcohol, stirring at a constant temperature of 80 ℃ until the solution is clear and has no macroscopic particles, and adjusting the pH to 8 by using ammonia water to obtain a polyvinyl alcohol solution for later use.
2.2 mixing 10 parts by weight of hydrophilic nano SiO2Adding aerogel into 150ml of absolute ethyl alcohol, performing ultrasonic dispersion for 5min, then adding 0.1 part by weight of gamma-methacryloxypropyltriethoxysilane and 5 parts by weight of deionized water, reacting at a constant temperature of 60 ℃ for 24h, stirring at a speed of 4000r/min in the reaction process, filtering out a solid product after the reaction is finished, drying, and grinding into powder to obtain the modified nano SiO2And then standby.
2.3 mixing 15 weight parts of dimethyl silicone oil, 4.5 weight parts of TEOS and 1.3 weight parts of modified nano SiO prepared in step 2.22Adding into a stirrer, mixing at 500r/min, adding the polyvinyl alcohol solution prepared in step 2.1 and 0.4 weight part of mineral oil defoaming agent, and shearing and emulsifying at 10000r/min for 10min by using an emulsifying machine to obtain water-based microcapsule emulsion (refer to figure 1) for use.
3. Preparation of polymer cement waterproof coating:
3.1 placing 85 parts by weight of Portland cement, 23 parts by weight of talcum powder, 65 parts by weight of fine quartz sand, 1 part by weight of carbon fiber, 0.32 part by weight of tartaric acid and 0.15 part by weight of the hydrophobically modified graphene oxide prepared in the step 1.2 of the embodiment in a stirrer, and mixing at the speed of 500r/min for 30min to obtain powder.
3.2 placing 55 parts by weight of emulsion, 18 parts by weight of deionized water, 1.8 parts by weight of film-forming assistant, 7 parts by weight of the aqueous microcapsule emulsion prepared in the step 2.3 of the embodiment, 1.4 parts by weight of hindered amine light stabilizer and 0.6 part by weight of preservative into a cement paste mixer, stirring at a low speed (67r/min) for 4min, and then stirring at a high speed (125r/min) for 5min to obtain a liquid material.
3.3, evenly adding the powder prepared in the step 3.1 into the liquid material prepared in the step 3.2 for 3 times, stirring at a low speed (67r/min) for 3min, then stirring at a high speed (125r/min) for 5min, adding 0.5 part by weight of mineral oil defoaming agent after the stirring is finished, and stirring at a low speed (67r/min) for 5min to obtain the super-hydrophobic microcapsule polymer cement-based anticorrosive coating.
First test example
The preparation method of the super-hydrophobic microcapsule polymer cement-based anticorrosive paint comprises the following steps:
1. preparation of aqueous microcapsule emulsion:
1.1 mixing 23 parts by weight of deionized water with 1.6 parts by weight of polyvinyl alcohol, then stirring at a constant temperature of 70 ℃ until the solution is clear and has no visible particles, and adjusting the pH to 8 by using ammonia water to obtain the polyvinyl alcohol solution for later use.
1.2 mixing 8 weight parts of hydrophilic nano SiO2Adding aerogel into 120ml of absolute ethyl alcohol, performing ultrasonic dispersion for 5min, then adding 1.5 parts by weight of hexamethyldisilazane and 5 parts by weight of deionized water, reacting for 20h at a constant temperature of 40 ℃, stirring at a speed of 2000r/min in the reaction process, filtering a solid product after the reaction is finished, drying and grinding into powder to obtain the modified nano SiO2And then standby.
1.3 mixing 10 parts by weight of simethicone and 5 parts by weight of simethiconeTEOS, 1.2 weight parts of modified nano SiO prepared in step 1.22Adding into a stirrer, uniformly mixing at the rotating speed of 700r/min, adding the polyvinyl alcohol solution prepared in the step 1.1 and 0.5 part by weight of organic silicon defoamer, and shearing and emulsifying for 8min at the speed of 5000r/min by using an emulsifying machine to obtain the water-based microcapsule emulsion for later use.
2. Preparation of polymer cement waterproof coating:
2.1 putting 70 parts by weight of Portland cement, 22 parts by weight of calcium carbonate, 65 parts by weight of fine quartz sand, 0.6 part by weight of steel fiber and 0.2 part by weight of retarder into a stirrer, and mixing for 20min at the speed of 500r/min to obtain powder.
2.2 placing 50 parts by weight of emulsion, 17 parts by weight of deionized water, 1.1 parts by weight of film-forming auxiliary agent, 6 parts by weight of the aqueous microcapsule emulsion prepared in the step 1.3 of the embodiment, 0.5 part by weight of benzotriazole light stabilizer and 0.3 part by weight of preservative into a cement paste mixer, stirring at a low speed (60r/min) for 4min, and then stirring at a high speed (120r/min) for 8min to obtain a liquid material.
2.3, evenly adding the powder prepared in the step 2.1 into the liquid material prepared in the step 2.2 for 3 times, then stirring at a low speed (60r/min) for 2min, then stirring at a high speed (120r/min) for 10min, adding 0.8 part by weight of an organic silicon defoaming agent after completion, and stirring at a low speed (60r/min) for 5min to obtain the cement-based anticorrosive coating.
Second test example
The preparation method of the super-hydrophobic microcapsule polymer cement-based anticorrosive paint comprises the following steps:
1. preparing hydrophobic modified graphene oxide:
1.1 adding 5 parts by weight of graphene oxide into 150ml of absolute ethyl alcohol, and then carrying out ultrasonic dispersion for 2 hours to obtain a graphene oxide dispersion liquid.
1.2 adding 7 parts by weight of polyperfluoroalkyl siloxane into the graphene oxide dispersion liquid, adjusting the reaction temperature to 65 ℃ for reaction for 24 hours, and violently stirring at the speed of 8000r/min in the reaction process. And after the reaction is finished, carrying out vacuum filtration on the reaction solution, washing the solid product for 3 times, then carrying out vacuum drying at 50 ℃ for 12 hours, and grinding to obtain the hydrophobic modified graphene oxide for later use.
2. Preparation of polymer cement waterproof coating:
2.1 placing 70 parts by weight of Portland cement, 22 parts by weight of calcium carbonate, 65 parts by weight of fine quartz sand, 0.6 part by weight of steel fiber, 0.2 part by weight of retarder and 0.2 part by weight of the hydrophobically modified graphene oxide prepared in the step 1.2 of the embodiment into a stirrer, and mixing at the speed of 500r/min for 20min to obtain powder.
2.2 placing 50 parts by weight of emulsion, 17 parts by weight of deionized water, 1.1 parts by weight of film-forming additive, 0.5 part by weight of benzotriazole light stabilizer and 0.3 part by weight of preservative into a cement paste mixer, stirring at a low speed (60r/min) for 4min, and then stirring at a high speed (120r/min) for 8min to obtain a liquid material.
2.3, evenly adding the powder prepared in the step 2.1 into the liquid material prepared in the step 2.2 for 3 times, then stirring at a low speed (60r/min) for 2min, then stirring at a high speed (120r/min) for 10min, adding 0.8 part by weight of an organic silicon defoaming agent after completion, and stirring at a low speed (60r/min) for 5min to obtain the cement-based anticorrosive coating.
Third test example
The preparation method of the super-hydrophobic microcapsule polymer cement-based anticorrosive paint comprises the following steps:
1. preparing hydrophobic modified graphene oxide:
1.1 adding 5 parts by weight of graphene oxide into 150ml of absolute ethyl alcohol, and then carrying out ultrasonic dispersion for 2 hours to obtain a graphene oxide dispersion liquid.
1.2 adding 7 parts by weight of polyperfluoroalkyl siloxane into the graphene oxide dispersion liquid, adjusting the reaction temperature to 65 ℃ for reaction for 24 hours, and violently stirring at the speed of 8000r/min in the reaction process. And after the reaction is finished, carrying out vacuum filtration on the reaction solution, washing the solid product for 3 times, then carrying out vacuum drying at 50 ℃ for 12 hours, and grinding to obtain the hydrophobic modified graphene oxide for later use.
2. Preparation of polymer cement waterproof coating:
2.1 placing 70 parts by weight of Portland cement, 22 parts by weight of calcium carbonate, 65 parts by weight of fine quartz sand, 0.6 part by weight of steel fiber, 0.2 part by weight of retarder and 0.2 part by weight of the hydrophobically modified graphene oxide prepared in the step 1.2 of the embodiment into a stirrer, and mixing at the speed of 500r/min for 20min to obtain powder.
2.2 placing 50 parts by weight of emulsion, 17 parts by weight of deionized water, 1.1 parts by weight of film forming additive, 2.4 parts by weight of dimethyl silicone oil, 0.8 part by weight of TEOS, 0.5 part by weight of benzotriazole light stabilizer and 0.3 part by weight of preservative into a cement paste mixer, stirring for 4min at a low speed (60r/min), and then stirring for 8min at a high speed (120r/min) to obtain a liquid material.
2.3, evenly adding the powder prepared in the step 2.1 into the liquid material prepared in the step 2.2 for 3 times, then stirring at a low speed (60r/min) for 2min, then stirring at a high speed (120r/min) for 10min, adding 0.8 part by weight of an organic silicon defoaming agent after completion, and stirring at a low speed (60r/min) for 5min to obtain the cement-based anticorrosive coating.
Performance testing
The performance of the cement-based anticorrosive coatings prepared in the above examples and test examples was intelligently tested, and the results are shown in tables 1 and 2.
TABLE 1
Figure BDA0002639299170000151
TABLE 2
Figure BDA0002639299170000152
As can be seen from tables 1 and 2, the anti-permeability performance and the water-impermeable time of the coating obtained by adding the hydrophobically modified graphene oxide in the first to fourth embodiments are significantly improved, and the water absorption rate is also significantly reduced, compared to the first test example without adding the hydrophobically modified graphene oxide. In addition, as can also be seen from the water repellency test of fig. 2, the surface of the coating material prepared in the first example did not adhere to water droplets, and it is also demonstrated that the coating material prepared in the example has good water repellency. The reason is that the uniformly distributed flaky graphene oxide cuts off capillary channels in the coating, prolongs the transmission path of water in the coating, and obviously improves the impermeability and water impermeability of the polymer cement coating.
As shown in FIG. 3, the aqueous microcapsule emulsion prepared in the above example is core-shell structure latex particles, which are distributed in the water phase, and the latex particles are made of SiO2The gel is used as a shell layer to be wrapped in SiO2The hydrophobic material in the gel shell layer is a core-shell structure formed by a core. And SiO2The hydrophobic material coated by the gel shell layer is slowly released after the coating is formed into a film, so that adverse effects on the polymer in the film forming process can be effectively avoided.
Further, with continued reference to tables 1 and 2, compared to the second test example without adding the aqueous microcapsule emulsion, the hydrophobic properties of the coatings obtained by adding the hydrophobically modified graphene oxide in the first to fourth examples are significantly improved, and the superhydrophobic level is reached. While the third test example is a coating obtained by directly adding a water repellent to a polymer cement material, it can be seen from the table that the tensile properties of the third test example are reduced to 2.54MPa, the adhesive strength is reduced to 2.53MPa, and the mechanical properties of the coatings obtained in the first to fourth examples are not reduced. This is because the hydrophobic material is used as a core, SiO2After the water-based microcapsule emulsion with gel as a shell layer is doped with the polymer cement waterproof coating, the adverse effects on the cement hydration hardening process and the polymer film forming process are avoided.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (14)

1. The super-hydrophobic microcapsule polymer cement-based anticorrosive paint comprises the following raw materials:
Figure DEST_PATH_IMAGE002
wherein the water-based microcapsule emulsion takes hydrophobic material as a core and SiO2The gel is a core-shell structure formed by a shell layer;
the emulsion comprises one or more of polyacrylate emulsion, ethylene-vinyl acetate copolymer emulsion and neoprene emulsion.
2. The anticorrosive paint according to claim 1, further comprising 0.5 to 0.8 parts by weight of an antifoaming agent; or, further comprises 20-25 parts by weight of a filler.
3. The anticorrosive paint according to claim 2, wherein the defoaming agent comprises any one or more of a silicone defoaming agent and a mineral oil defoaming agent.
4. The anticorrosive paint according to claim 2, wherein the filler comprises any one or more of calcium carbonate powder, mica powder and silica powder.
5. The anticorrosive paint according to claim 1, wherein the cement comprises any one of portland cement and sulphoaluminate cement;
or the reinforcing agent is fiber, and comprises one or more of polypropylene fiber, steel fiber and carbon fiber;
alternatively, the set retarder comprises one or more of tartaric acid, citric acid, and boric acid;
or the light stabilizer comprises one or more of benzophenones, benzotriazole and hindered amine;
alternatively, the preservative comprises one or more of sodium pentachlorophenol, TPN (2,4,5, 6-tetrachloroisophthalonitrile), TBZ (2- (4-thiazolyl) benzimidazole).
6. The anticorrosive paint according to any one of claims 1 to 5, wherein the hydrophobically modified graphene oxide is a fluorosilane hydrophobizing agent modified graphene oxide.
7. The anticorrosive paint of any one of claims 1 to 5, wherein the hydrophobic material in the aqueous microcapsule emulsion comprises any one or more of dimethicone and polymethylhydrosiloxane.
8. The method for preparing the anticorrosive paint according to any one of claims 1 to 7, characterized by comprising the steps of:
preparing hydrophobic modified graphene oxide:
(1) mixing graphene oxide and a volatile solvent, and then carrying out ultrasonic dispersion to obtain a graphene oxide dispersion liquid for later use;
(2) adding fluorosilane into the graphene oxide dispersion liquid, stirring while reacting under a heating condition, and washing, drying and grinding the obtained product in sequence after the reaction is finished to obtain the hydrophobically modified graphene oxide for later use;
preparation of aqueous microcapsule emulsion:
(3) mixing water and polyvinyl alcohol, stirring the mixture under the condition of constant temperature and heat preservation until the mixture is clear and has no visible particles, and then adjusting the mixture to be alkaline by using ammonia water to obtain a polyvinyl alcohol solution for later use;
(4) hydrophilic nano SiO2Mixing aerogel and volatile solvent, performing ultrasonic dispersion, adding a hydrophobic modifier with one hydrophilic end and one lipophilic end and water, stirring and reacting under the condition of constant temperature and heat preservation, separating out a solid product after the reaction is finished, drying and grinding the solid product to obtain modified nano SiO2And is ready for use;
(5) hydrophobic agent, ethyl orthosilicate and the modified nano SiO in the step (4)2Uniformly mixing, adding the polyvinyl alcohol solution obtained in the step (3) and a defoaming agent, and then shearing and emulsifying to obtain a water-based microcapsule emulsion;
preparation of polymer cement waterproof coating:
(6) uniformly mixing cement, calcium carbonate, quartz sand, a reinforcing agent, a retarder and the hydrophobic modified graphene oxide prepared in the step (2) to obtain a first mixture for later use;
(7) uniformly mixing the emulsion, water, a film-forming auxiliary agent, the aqueous microcapsule emulsion prepared in the step (5), a light stabilizer and a preservative to obtain a second mixture for later use;
(8) and adding the first mixture into the second mixture in batches, uniformly stirring, adding the defoaming agent, and uniformly stirring to obtain the super-hydrophobic microcapsule polymer cement-based anticorrosive coating.
9. The method for preparing the anticorrosive paint according to claim 8, wherein in the step (1), the volatile solvent is absolute ethyl alcohol;
or, in the step (1), the time of ultrasonic dispersion is 1-2 h;
or in the step (2), the fluorosilane is added in a proportion of 3-5 parts by weight of graphene oxide and 4.5-7.5 parts by weight of fluorine-containing silane;
or in the step (2), the fluorosilane comprises any one of tridecafluorooctyltriethoxysilane, polyperfluoroalkylsiloxane, tridecafluorooctyltrimethoxysilane and heptadecafluorodecyl;
or, in the step (2), the heating temperature is 60-80 ℃, the reaction time is 20-24h, and the stirring speed is 5000-;
or, in the step (2), the washing mode is vacuum filtration washing for 2-3 times, and the drying mode is as follows: vacuum drying at 50-60 deg.C for 8-12 h.
10. The preparation method of the anticorrosive paint according to claim 8, wherein in the step (3), the water and the polyvinyl alcohol are added in the following proportion of 20-30 parts by weight: 1-2 parts by weight;
or in the step (3), the constant temperature is kept at 50-80 ℃;
or, in the step (3), the alkaline pH is 8-9;
or, in the step (4), the volatile solvent is absolute ethyl alcohol;
or, in the step (4), the hydrophilic nano SiO2The addition proportions of the aerogel, the hydrophobic modifier and the water are 5-10 parts by weight in sequence: 0.1-2 parts by weight: 3-5 parts by weight;
or, in the step (4), the modifier comprises one or more of hexamethyldisilazane, gamma-methacryloxypropyl, stearic acid, trichloromethylsilane, octadecyltriethoxysilane and octadecyltrichlorosilane;
or, in the step (4), the ultrasonic dispersion time is 3-5min, the constant temperature heat preservation time is 40-60 ℃, the stirring speed is 2000-4000r/min, and the reaction time is 12-24 h;
or, in the step (5), the hydrophobic agent, ethyl orthosilicate and modified nano SiO2The addition proportions of the polyvinyl alcohol and the defoaming agent in the polyvinyl alcohol solution are as follows: 8-15 parts by weight, 3-5 parts by weight, 0.5-1.5 parts by weight, 1-2 parts by weight and 0.3-0.5 parts by weight;
or, in the step (5), the rotation speed of the shearing emulsification is 8000-;
or, in the step (5), the hydrophobic agent comprises any one or more of simethicone and polymethylhydrosiloxane.
11. The preparation method of the anticorrosive paint according to claim 10, characterized in that 5-10 parts by weight of hydrophilic nano SiO2When the aerogel is prepared, 100ml of anhydrous ethanol is taken.
12. The method for preparing anticorrosive paint according to claim 10, wherein the solid product is separated by filtration in step (4).
13. The method for preparing an anticorrosive paint according to any one of claims 8 to 12, wherein in step (6), the mixing is performed in such a manner that: mixing at 400-500r/min for 20-30 min;
or, in the step (7), the uniformly mixing mode is as follows: mixing at 57-67r/min for 3-4min, and then mixing at 115-135r/min for 5-10 min;
or, in the step (8), the stirring uniformly mode is as follows: adding the first mixture into the second mixture for 2-3 times, stirring at 57-67r/min for 2-3min, stirring at 115-135r/min for 5-10min, adding defoaming agent, and stirring at 57-67r/min for 3-5 min;
or in the steps (5) and (8), the defoaming agent comprises any one or more of an organic silicon defoaming agent and a mineral oil defoaming agent.
14. Use of the superhydrophobic microcapsule polymer cement-based anticorrosive coating of any one of claims 1 to 7 or prepared by the method of any one of claims 8 to 13 in the fields of bathrooms, kitchens, exterior walls of buildings, marine engineering, underground engineering.
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