CN113817408B - Waterproof coating, modified silane and application of modified silane in preparation of waterproof coating - Google Patents

Waterproof coating, modified silane and application of modified silane in preparation of waterproof coating Download PDF

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CN113817408B
CN113817408B CN202111169219.0A CN202111169219A CN113817408B CN 113817408 B CN113817408 B CN 113817408B CN 202111169219 A CN202111169219 A CN 202111169219A CN 113817408 B CN113817408 B CN 113817408B
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particles
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weight
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CN113817408A (en
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刘世波
王春雨
何历超
白至阳
路成真
周武
王硕
刘昕
李建涛
曹江明
武天宇
张晗
臧宏阳
李振山
张桁
李俊忠
傅庆志
李冰
聂雷
孙维龙
安宏飞
聂洪超
李会强
田占军
葛喜瑞
赵雪璞
史剑
金增华
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Beijing Ligao Lide Engineering Technology 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

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Abstract

The invention discloses a waterproof coating, modified silane and application thereof in preparing the waterproof coating, wherein the waterproof coating comprises the following components: modified silane, photosensitive resin, heat insulation filler and tetrahydrofuran. Wherein the modified silane is prepared by modifying silane by adopting amphiphilic particles. The waterproof coating prepared by the invention has excellent waterproof performance, weather resistance and carbonization corrosion resistance.

Description

Waterproof coating, modified silane and application of modified silane in preparation of waterproof coating
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a waterproof coating, modified silane and application of the waterproof coating in preparation of the waterproof coating.
Background
Due to the chemical composition and structural characteristics of concrete, concrete is extremely susceptible to corrosive media. The corrosion of concrete buildings generally causes the damage and deterioration of concrete under the action of environmental factors, such as long-time exposure, rain, industrial pollutants and the like, which can cause the carbonization of concrete or the corrosion of steel structures, and the problems of cracking, expansion, peeling and the like. The protective coating is coated on the surface of the concrete, so that the concrete can be waterproof, anticorrosive and anti-aging, the durability is improved, and the service life is prolonged. Chinese patent CN107216747A discloses a nanotechnology protective coating for a concrete steel structure and a preparation method thereof, wherein the nanotechnology protective coating comprises the following raw materials: acrylic resin, amino resin, epoxy modified chlorinated high polymer, nano composite preservative mother liquor, pentaerythritol or dipentaerythritol, ammonium polyphosphate, reinforced glass fiber, titanium pigment and defoaming agent. The protective coating of the patent improves the oil resistance and salt spray corrosion resistance of the coating by using a material compounding technology and a nano modification technology, has strong adhesive force, is convenient for spraying and brushing construction, but has poor weather resistance, carbonization resistance and aging resistance in use. Chinese patent CN109705697A discloses a concrete coating, which comprises the following components: the coating comprises water-based acrylic modified epoxy resin, a silane coupling agent, deionized water, quartz sand, scales, chopped fibers, a film-forming auxiliary agent, a dispersing agent, a flatting agent, a defoaming agent, a thickening agent, a drier and a pigment. The concrete coating of the patent guarantees the appearance of a concrete building, prolongs the service performance and durability of the building, and needs to be improved in carbonization corrosion resistance and aging resistance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a waterproof coating, modified silane and application in preparing the waterproof coating.
The preparation method of the modified silane comprises the following steps:
s1, adding silane monomers into an organic solvent A according to the weight ratio of (1-3) to (4-7), and stirring and dispersing at 150-200rpm for 30-60min to obtain an organic silicon solution;
s2, under the dark condition, adding the amphiphilic particles into the organic solvent A according to the material-liquid ratio (1-3) g (15-30) mL, and carrying out ultrasonic-assisted dispersion at 25-40kHz and 200-400W for 30-60min to obtain a particle dispersion liquid;
s3, under the dark condition, mixing the organic silicon solution and the particle dispersion according to the weight ratio of (6-10) to (1-2), and stirring at the speed of 300-600rpm for 20-40min to obtain the modified silane.
The silane monomer is at least one selected from methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane and hexadecyltrimethoxysilane.
The organic solvent A is selected from any one of n-butanol, tetrahydrofuran, acetone and butyl acetate.
The organic silicon coating has low reaction activity and strong permeability, and can hydrolyze out high-activity silicon hydroxyl groups by utilizing silane bonds and condense with hydroxyl groups on the surface of concrete to form a hydrophobic coating. But can only form a film on the surface of concrete and in the inner wall of a pore, and can not seal the defects of the pore and a crack. The epoxy acrylate resin photosensitive material is added, so that the obtained coating has permeability and can be solidified to form a film, a compact protective layer is formed on the surface layer of concrete, the defects of pores and cracks are sealed, and the protective effect is improved. However, the coating is dense, so that water vapor is not easy to discharge, or atmospheric pollutants can corrode concrete while partial water vapor is discharged, and the protection effect is still insufficient.
PEDOT in the amphiphilic particles is a hydrophobic structure and has conductivity and film-forming property. Due to the interaction of attractive force among the particles, PEDOT is easy to aggregate around titanium dioxide to form a firework-shaped cluster, the cluster structure is outward from the titanium dioxide side and inward from the PEDOT side, and the hydrophilicity is improved. The titanium dioxide has higher photocatalytic activity, can provide kinetic energy required by the particles to move autonomously under the irradiation of ultraviolet light, and does self-propulsion movement, and the diffusion coefficient is large, so that cluster particles are dispersed. Under the irradiation of ultraviolet light, the curing and film forming of the coating also occur simultaneously. Because the distance between the cluster structure and the surface of the film is different, the degree of ultraviolet irradiation is different, and the kinetic energy obtained by the particles is different, so that the cluster degree at different distances from the surface of the film is different, the closer to the surface of the film, the smaller the cluster degree is, the more uniform the particle distribution is, the better the film forming property is, and the higher the hydrophobicity is; and the film forming property and the hydrophobicity are gradually reduced from the surface of the film to the concrete base surface, a dendriform branched gradient structure is formed, self-driven directional air guiding and water guiding can be realized, water and gas on the concrete base surface are led out, and the corrosion of the external atmosphere of the film coating to the concrete is prevented. Due to the combination of the titanium dioxide photocatalysis effect and the PEDOT conductivity, the addition of the amphiphilic particles also has the electrical corrosion prevention effect, and the effect of preventing concrete corrosion is improved.
The preparation method of the amphiphilic particles comprises the following steps:
K1. modified TiO is added2Adding the particles into carbon tetrabromide at 90-95 ℃ according to the material-liquid ratio of 1g (20-30) mL, and ultrasonically dispersing for 30-60min at 100-300W and 30-50kHz to obtain the modified TiO2A particulate floating liquid;
K2. adding EDOT into water with the temperature of 90-95 ℃ according to the material-liquid ratio of 1 (30-50), and ultrasonically dispersing for 20-30min at 100-300W and 30-50kHz to obtain EDOT suspension;
K3. adding EDOT suspension into the modified TiO obtained in the step of K1 according to the weight ratio of 1 (3-5)2Floating the particles in the liquid to obtain a mixed liquid;
K4. keeping the temperature at 90-95 ℃ and adding Na (20-25) to the mixed solution by weight ratio (1-2)2S2O8And FeCl3In which Na is2S2O8The material-liquid ratio of the mixed solution is 1g (300-400) mL, the mixture is stirred for 1-2min at the rotation speed of 900rpm of 700-400-;
K5. and filtering the reaction mixture while the reaction mixture is hot, and sequentially washing with alcohol, water and drying to obtain the amphiphilic particles.
Modified TiO2The space volume of the particles is increased, the density is reduced, the particles float on the liquid level of carbon tetrabromide, the titanium dioxide is an amphiphilic material, the surface of the titanium dioxide generally contains a large amount of hydroxyl groups and shows hydrophilicity, and the surface active modifier endows modified TiO with2Better pair of granulesHydrophilic and oleophilic, after EDOT suspension is added, because carbon tetrabromide is not dissolved with water and the density is far larger than that of water, the mixed solution is layered and is compared with unmodified TiO2Particles of modified TiO2The particles are better suspended between the layered interfaces. Modified TiO in EDOT suspension2The particles float above the liquid. Na (Na)2S2O8And FeCl3After being added, the mixture is quickly stirred and dissolved in EDOT suspension liquid on the upper layer to initiate EDOT polymerization to generate PEDOT, and the PEDOT is downwards deposited on a layered interface and is coated on modified TiO2The upper surface of the particle self-assembles into a shell, generating the asymmetric amphiphilic microparticle.
The modified TiO2The preparation method of the particles comprises the following steps:
t1, dissolving tetrabutyl titanate in absolute ethyl alcohol according to the weight ratio of 1 (3-6) to obtain a solution A;
t2, dissolving a surface active modifier in a (10-14) wt% acetic acid aqueous solution according to a material-to-liquid ratio (1-2) g:1000mL to obtain a solution B;
t3, stirring the solution A at the rotation speed of 100-;
t4, placing the reactant in a muffle furnace, heating to 400-600 ℃ at the heating rate of 5-6 ℃/min, roasting for 3-5h, and naturally cooling to room temperature to obtain the modified TiO2And (3) granules.
The surface active modifier is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, monolauryl phosphate and disodium lauryl sulfosuccinate monoester.
Preferably, the surface active modifier consists of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate in the weight ratio of (1-2) to (1-3).
Surface active modifiers impart modified TiO2The particles have better amphiphilicity, which is beneficial to improving the compatibility of the amphiphilic particles and silane. Sodium dodecyl benzene sulfonate modified TiO2The granules increase the granule spaceVolume, reduced density, modified TiO2The particles can better float on a layered interface, and modified TiO is added by utilizing the high HLB value and strong hydrophilicity of the sodium dodecyl sulfate2Hydrophilic functional group of particle, promote modified TiO2The hydrophilicity of the particles is also beneficial to modifying TiO2The floating of the particles on the layered interface and the synergistic effect of the particles lead the asymmetric effect of the prepared amphiphilic particles to be better and the dispersion effect to be better when the particles are irradiated by ultraviolet light. And due to amphiphilic fine particles of TiO2The difference between the hydrophilic and hydrophobic effects of the side and the PEDOT side is increased, and the cluster structure is higher in hydrophilicity, so that the self-driven directional air guiding and water guiding effect in the using process of the coating is improved.
The invention also provides application of the modified silane in preparation of waterproof coatings.
The waterproof coating comprises the following components in parts by weight: 30-50 parts of the modified silane, 12-20 parts of photosensitive resin and 15-20 parts of tetrahydrofuran.
Preferably, the waterproof coating comprises the following components in parts by weight: 30-50 parts of modified silane, 12-20 parts of photosensitive resin, 3-8 parts of heat insulation filler and 15-20 parts of tetrahydrofuran.
The preparation method of the heat insulation filler comprises the following steps:
adding 2-5 parts by weight of aluminum nitrate into 15-30 parts by weight of 80-90wt% ethanol aqueous solution, uniformly mixing, adding 1-3 parts by weight of cerium nitrate and 5-8 parts by weight of tripropyl borate, heating at 90-110 ℃ for 2-4h, performing microwave treatment at 600-800W and 70-80 ℃ for 1-3h, centrifuging and drying to obtain an inorganic compound; adding 1-2 parts of sodium lauryl sulfonate into 100-120 parts of 0.05-0.1wt% acetic acid aqueous solution, uniformly mixing, then adding 18-22 parts of urea, stirring at 25-30 ℃ and 100-200rpm for 20-40min, then adding 70-90 parts of n-propyl trimethoxy silane, and continuously stirring for 30-50min to obtain SiO2Sol; adding 3-5 parts of inorganic compound and 1-2 parts of silicon nitride into the SiO2Stirring the sol for 2 to 3 hours at the temperature of between 25 and 30 ℃ and at the speed of 100 and 200rpm, then standing the sol for 5 to 10 hours, centrifuging the sol and drying the sol to obtain the heat-insulating filler.
According to the invention, through adding amphiphilic particles into silane for modification, the one-way water and gas guiding function is realized, the coating is mixed with photosensitive resin to comprehensively adjust the waterproof and gas permeability, the excessive moisture of the concrete can be discharged, and the concrete neutralization caused by the erosion of the concrete by harmful components in the air is avoided.
The photosensitive resin comprises the following components in parts by weight: 20-40 parts of epoxy acrylate resin, 20-30 parts of butyl acrylate and 1-3 parts of bibenzoyl.
The epoxy acrylate resin is selected from any one of bisphenol A epoxy acrylate resin and epoxidized soybean oil acrylate.
The preparation method of the waterproof coating comprises the following steps: and (3) stirring and uniformly mixing the modified silane, the photosensitive resin, the heat-insulating filler and the tetrahydrofuran under the dark condition to obtain the composite material.
The invention has the beneficial effects that: the waterproof coating prepared by the invention has good heat insulation effect, and also has excellent waterproof performance, weather resistance and carbonization corrosion resistance. One of the components is modified silane, which is prepared by modifying silane by adopting amphiphilic particles, and the silane is matched with photosensitive resin, and the silane and the photosensitive resin are combined with consolidation film forming capability and permeability resistance, so that the waterproof and air-proof protection effect is realized, and the self-driven directional air guide and water guide effect can be achieved. The moisture on the concrete base surface is easy to be led out, thereby effectively preventing the corrosion of the atmosphere outside the coating film to the concrete and improving the performance of the concrete.
Detailed Description
Some of the raw materials are introduced as follows:
the photosensitive resin comprises the following components in parts by weight: 28 parts of bisphenol A epoxy acrylate resin, 22 parts of butyl acrylate and 1.2 parts of bibenzoyl.
Bisphenol a epoxy acrylate resin, available from jinan quanxing new materials ltd, viscosity: 40000-60000 (cps/25 ℃).
Bibenzoyl, CAS No.: 134-81-6.
EDOT, chinese name: 3, 4-ethylenedioxythiophene, CAS No.: 126213-50-1.
Preparation example 1
The preparation method of the modified silane comprises the following steps:
s1, adding dimethyl dimethoxy silane into tetrahydrofuran according to the weight ratio of 2:5, and stirring and dispersing for 50min at 200rpm to obtain an organic silicon solution;
s2, adding the amphiphilic particles into tetrahydrofuran according to the material-liquid ratio of 2g:20mL under the dark condition, and performing ultrasonic assisted dispersion at 30kHz and 300W for 40min to obtain a particle dispersion liquid;
and S3, mixing the organic silicon solution and the particle dispersion liquid according to the weight ratio of 7:1 under the dark condition, and stirring at 500rpm for 30min to obtain the modified silane.
The preparation method of the amphiphilic particles comprises the following steps:
K1. modified TiO2Adding the particles into 92 ℃ carbon tetrabromide according to the feed-liquid ratio of 1g:22mL, and ultrasonically dispersing for 40min at 200W and 35kHz to obtain modified TiO2Floating liquid on the particles;
K2. adding EDOT into 92 ℃ water according to the weight ratio of 1:35, and ultrasonically dispersing for 25min at 200W and 35kHz to obtain EDOT suspension;
K3. adding EDOT suspension into the modified TiO obtained in the step of K1 according to the weight ratio of 1:32Floating the particles in the liquid to obtain a mixed liquid;
K4. while keeping the temperature at 92 ℃, Na with the weight ratio of 23:1.4 is added into the mixed solution2S2O8And FeCl3In which Na is2S2O8The material-liquid ratio of the mixed solution is 1g:360mL, the mixture is stirred for 1.5min at 800rpm immediately after the mixture is added, the stirring is stopped, and the mixture is kept warm and kept stand for reaction for 16h to obtain a reaction mixture;
K5. and filtering the reaction mixture while the reaction mixture is hot, and sequentially washing with alcohol, water and drying to obtain the amphiphilic particles.
The modified TiO2The preparation method of the particles comprises the following steps:
t1, dissolving tetrabutyl titanate in absolute ethyl alcohol according to the weight ratio of 1:5 to obtain a solution A;
t2, dissolving a surface active modifier in a 12wt% acetic acid aqueous solution according to a material-to-liquid ratio of 1g:1000mL to obtain a solution B;
t3, stirring the solution A at the rotating speed of 150rpm, simultaneously dropwise adding the solution B into the solution A at the speed of 4mL/min, wherein the weight ratio of the solution A to the solution B is 1:1.2, continuously stirring for 30min after dropwise adding, standing for 2d, drying at 110 ℃, grinding, and sieving with a 800-mesh sieve to obtain a reactant;
t4, placing the reactant in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, roasting for 4h, and naturally cooling to room temperature to obtain the modified TiO2And (3) particles.
The surface active modifier is prepared from sodium dodecyl benzene sulfonate and sodium dodecyl sulfate according to the weight ratio of 1:1.
Preparation example 2
The preparation method of the modified silane comprises the following steps:
s1, adding dimethyl dimethoxysilane into tetrahydrofuran according to the weight ratio of 2:5, and stirring and dispersing for 50min at 200rpm to obtain an organic silicon solution;
s2, under the condition of keeping out of the sun, adding TiO2Adding the particles into tetrahydrofuran according to the ratio of 2g to 20mL of the feed liquid, and performing ultrasonic-assisted dispersion at 30kHz and 300W for 40min to obtain a particle dispersion liquid;
and S3, mixing the organic silicon solution and the particle dispersion liquid according to the weight ratio of 7:1 under the dark condition, and stirring at 500rpm for 30min to obtain the modified silane.
The TiO is2The preparation method of the particles comprises the following steps:
t1, dissolving tetrabutyl titanate in absolute ethyl alcohol according to the weight ratio of 1:5 to obtain a solution A;
t2, stirring the solution A at the rotating speed of 150rpm, simultaneously dropwise adding 12wt% of acetic acid aqueous solution into the solution A at the speed of 4mL/min, wherein the weight ratio of the solution A to the acetic acid aqueous solution is 1:1.2, continuously stirring for 30min after the dropwise adding is finished, standing for 2d, drying at 110 ℃, grinding and sieving by using a 800-mesh sieve to obtain a reactant;
t3, placing the reactant in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, roasting for 4h, and naturally cooling to room temperature to obtain TiO2And (3) granules.
Preparation example 3
The preparation method of the modified silane comprises the following steps:
s1, adding dimethyl dimethoxysilane into tetrahydrofuran according to the weight ratio of 2:5, and stirring and dispersing for 50min at 200rpm to obtain an organic silicon solution;
s2, adding the amphiphilic particles into tetrahydrofuran according to a material-liquid ratio of 2g:20mL under a dark condition, and performing ultrasonic-assisted dispersion at 30kHz and 300W for 40min to obtain a particle dispersion liquid;
and S3, mixing the organic silicon solution and the particle dispersion liquid according to the weight ratio of 7:1 under the dark condition, and stirring at 500rpm for 30min to obtain the modified silane.
The preparation method of the amphiphilic particles comprises the following steps:
K1. modified TiO is added2Adding the particles into 92 ℃ carbon tetrabromide according to the feed-liquid ratio of 1g:22mL, and ultrasonically dispersing for 40min at 200W and 35kHz to obtain modified TiO2Floating liquid on the particles;
K2. adding EDOT into 92 ℃ water according to the weight ratio of 1:35, and performing ultrasonic dispersion on the EDOT at 200W and 35kHz for 25min to obtain EDOT suspension;
K3. adding EDOT suspension into the modified TiO obtained in the step of K1 according to the weight ratio of 1:32Floating the particles in the liquid to obtain a mixed liquid;
K4. while keeping the temperature at 92 ℃, adding Na with the weight ratio of 23:1.4 into the mixed solution2S2O8And FeCl3In which Na is2S2O8The material-liquid ratio of the mixed solution to the mixed solution is 1g:360mL, the mixed solution is stirred for 1.5min at the rotation speed of 800rpm immediately after the addition, the stirring is stopped, and the mixed solution is kept warm and stands for reaction for 16h to obtain a reaction mixture;
K5. and filtering the reaction mixture while the reaction mixture is hot, and sequentially washing with alcohol, water and drying to obtain the amphiphilic particles.
The modified TiO2The preparation method of the particles comprises the following steps:
t1, dissolving tetrabutyl titanate in absolute ethyl alcohol according to the weight ratio of 1:5 to obtain a solution A;
t2, dissolving a surface active modifier in a 12wt% acetic acid aqueous solution according to the feed-liquid ratio of 1g:1000mL to obtain a solution B;
t3, stirring the solution A at the rotating speed of 150rpm, simultaneously dropwise adding the solution B into the solution A at the speed of 4mL/min, wherein the weight ratio of the solution A to the solution B is 1:1.2, continuously stirring for 30min after dropwise adding, standing for 2d, drying at 110 ℃, grinding, and sieving with a 800-mesh sieve to obtain a reactant;
and T4, placing the reactant in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, roasting for 4h, and naturally cooling to room temperature to obtain the modified TiO2And (3) granules.
The surface active modifier is sodium dodecyl benzene sulfonate.
Preparation example 4
The preparation method of the modified silane comprises the following steps:
s1, adding dimethyl dimethoxysilane into tetrahydrofuran according to the weight ratio of 2:5, and stirring and dispersing for 50min at 200rpm to obtain an organic silicon solution;
s2, adding the amphiphilic particles into tetrahydrofuran according to the material-liquid ratio of 2g:20mL under the dark condition, and performing ultrasonic assisted dispersion at 30kHz and 300W for 40min to obtain a particle dispersion liquid;
and S3, mixing the organic silicon solution and the particle dispersion liquid according to the weight ratio of 7:1 under the dark condition, and stirring at 500rpm for 30min to obtain the modified silane.
The preparation method of the amphiphilic particles comprises the following steps:
K1. modified TiO2Adding the particles into 92 ℃ carbon tetrabromide according to the feed-liquid ratio of 1g:22mL, and ultrasonically dispersing for 40min at 200W and 35kHz to obtain modified TiO2Floating liquid on the particles;
K2. adding EDOT into 92 ℃ water according to the weight ratio of 1:35, and ultrasonically dispersing for 25min at 200W and 35kHz to obtain EDOT suspension;
K3. adding EDOT suspension into the modified TiO obtained in the step of K1 according to the weight ratio of 1:32Floating the particles in the liquid to obtain a mixed liquid;
K4. while keeping the temperature at 92 ℃, adding Na with the weight ratio of 23:1.4 into the mixed solution2S2O8And FeCl3In which Na2S2O8The material-liquid ratio of the mixed solution to the mixed solution is 1g:360mL, the mixed solution is stirred for 1.5min at the rotation speed of 800rpm immediately after the addition, the stirring is stopped, and the mixed solution is kept warm and stands for reaction for 16h to obtain a reaction mixture;
K5. and filtering the reaction mixture while the reaction mixture is hot, and sequentially washing with alcohol, washing with water and drying to obtain the amphiphilic particles.
The modified TiO2The preparation method of the particles comprises the following steps:
t1, dissolving tetrabutyl titanate in absolute ethyl alcohol according to the weight ratio of 1:5 to obtain a solution A;
t2, dissolving a surface active modifier in a 12wt% acetic acid aqueous solution according to the feed-liquid ratio of 1g:1000mL to obtain a solution B;
t3, stirring the solution A at the rotating speed of 150rpm, simultaneously dropwise adding the solution B into the solution A at the speed of 4mL/min, wherein the weight ratio of the solution A to the solution B is 1:1.2, continuously stirring for 30min after dropwise adding, standing for 2d, drying at 110 ℃, grinding, and sieving with a 800-mesh sieve to obtain a reactant;
and T4, placing the reactant in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, roasting for 4h, and naturally cooling to room temperature to obtain the modified TiO2And (3) granules.
The surface active modifier is sodium dodecyl sulfate.
Preparation example 5
The preparation method of the modified silane comprises the following steps:
s1, adding dimethyl dimethoxy silane into tetrahydrofuran according to the weight ratio of 2:5, and stirring and dispersing for 50min at 200rpm to obtain an organic silicon solution;
s2, adding the amphiphilic particles into tetrahydrofuran according to the material-liquid ratio of 2g:20mL under the dark condition, and performing ultrasonic assisted dispersion at 30kHz and 300W for 40min to obtain a particle dispersion liquid;
and S3, mixing the organic silicon solution and the particle dispersion liquid according to the weight ratio of 7:1 under the dark condition, and stirring at 500rpm for 30min to obtain the modified silane.
The preparation method of the amphiphilic particles comprises the following steps:
K1. adding TiO into the mixture2Adding the particles into 92 ℃ water according to the feed-liquid ratio of 1g:22mL, and performing ultrasonic dispersion on the particles at 200W and 35kHz for 40min to obtain TiO2A particle dispersion;
K2. adding EDOT into 92 ℃ water according to the weight ratio of 1:35, and performing ultrasonic dispersion on the EDOT at 200W and 35kHz for 25min to obtain EDOT suspension;
K3. adding EDOT suspension into the modified TiO obtained in the step of K1 according to the weight ratio of 1:32Obtaining a mixed solution in the particle dispersion liquid;
K4. while keeping the temperature at 92 ℃, adding Na with the weight ratio of 23:1.4 into the mixed solution2S2O8And FeCl3In which Na is2S2O8The material-liquid ratio of the mixed solution is 1g:360mL, the mixture is stirred for 1.5min at 800rpm immediately after the mixture is added, the stirring is stopped, and the mixture is kept warm and kept stand for reaction for 16h to obtain a reaction mixture;
K5. and filtering the reaction mixture while the reaction mixture is hot, and sequentially washing with alcohol, water and drying to obtain the amphiphilic particles.
The TiO is2The preparation method of the particles comprises the following steps:
t1, dissolving tetrabutyl titanate in absolute ethyl alcohol according to the weight ratio of 1:5 to obtain a solution A;
t2, stirring the solution A at the rotating speed of 150rpm, simultaneously dropwise adding a 12wt% acetic acid aqueous solution into the solution A at the speed of 4mL/min, wherein the weight ratio of the solution A to the acetic acid aqueous solution is 1:1.2, continuously stirring for 30min after the dropwise adding is finished, standing for 2d, drying at 110 ℃, grinding and sieving by using a 800-mesh sieve to obtain a reactant;
t3, placing the reactant in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, roasting for 4h, and naturally cooling to room temperature to obtain TiO2And (3) particles.
Preparation example 6
The preparation method of the modified silane comprises the following steps:
s1, adding dimethyl dimethoxy silane into tetrahydrofuran according to the weight ratio of 2:5, and stirring and dispersing for 50min at 200rpm to obtain an organic silicon solution;
s2, mixing the organic silicon solution and tetrahydrofuran according to the weight ratio of 7:1 under the dark condition, and stirring at 500rpm for 30min to obtain the modified silane.
Example 1
The preparation method of the waterproof coating comprises the following steps: under the condition of keeping out of the sun, 35 parts by weight of the modified silane of preparation example 1, 16 parts by weight of photosensitive resin and 18 parts by weight of tetrahydrofuran are stirred and mixed uniformly to obtain the photosensitive resin.
Example 2
The preparation method of the waterproof coating comprises the following steps: under the condition of keeping out of the sun, according to the weight portion, 35 portions of the modified silane of the preparation example 2, 16 portions of the photosensitive resin and 18 portions of tetrahydrofuran are stirred and mixed evenly to obtain the photosensitive modified silane.
Example 3
The preparation method of the waterproof coating comprises the following steps: under the condition of keeping away from light, according to the weight portion, 35 portions of the modified silane of the preparation example 3, 16 portions of the photosensitive resin and 18 portions of tetrahydrofuran are stirred and mixed evenly to obtain the photosensitive modified silane.
Example 4
The preparation method of the waterproof coating comprises the following steps: under the condition of keeping out of the sun, 35 parts by weight of the modified silane of preparation example 4, 16 parts by weight of photosensitive resin and 18 parts by weight of tetrahydrofuran are stirred and mixed uniformly to obtain the photosensitive modified silane.
Example 5
The preparation method of the waterproof coating comprises the following steps: under the condition of keeping out of the sun, 35 parts by weight of the modified silane of preparation example 5, 16 parts by weight of photosensitive resin and 18 parts by weight of tetrahydrofuran are stirred and mixed uniformly to obtain the photosensitive modified silane.
Example 6
The preparation method of the waterproof coating comprises the following steps: under the condition of keeping out of the sun, according to the weight portion, 35 portions of the modified silane of the preparation example 6, 16 portions of the photosensitive resin and 18 portions of tetrahydrofuran are stirred and mixed evenly to obtain the photosensitive modified silane.
Example 7
The preparation method of the waterproof coating comprises the following steps: under the condition of keeping away from light, according to parts by weight, 35 parts of modified silane prepared in preparation example 1, 16 parts of photosensitive resin, 5 parts of heat insulation filler and 18 parts of tetrahydrofuran are stirred and mixed uniformly to obtain the modified silane.
The preparation method of the heat insulation filler comprises the following steps:
adding 1.2 parts of sodium lauryl sulfonate into 100 parts of 0.08wt% acetic acid aqueous solution, uniformly mixing, adding 20 parts of urea, stirring at 28 ℃ and 150rpm for 30min, adding 80 parts of n-propyl trimethoxy silane, and continuously stirring for 35min to obtain SiO2Sol; adding 1 part of silicon nitride into the SiO2Stirring the sol for 2.5h at 28 ℃ and 150rpm, standing for 8h, centrifuging and drying to obtain the heat-insulating filler. The heat insulation performance of the waterproof coating obtained in example 7 is evaluated according to the standard GB/T17371-2008, and the thermal conductivity is 0.089W/(mK).
Example 8
The preparation method of the waterproof coating comprises the following steps: under the condition of keeping away from light, according to parts by weight, 35 parts of modified silane prepared in preparation example 1, 16 parts of photosensitive resin, 5 parts of heat insulation filler and 18 parts of tetrahydrofuran are stirred and mixed uniformly to obtain the modified silane.
The preparation method of the heat insulation filler comprises the following steps:
adding 3 parts by weight of aluminum nitrate into 20 parts by weight of 85wt% ethanol aqueous solution, uniformly mixing, adding 2 parts by weight of cerium nitrate and 6 parts by weight of tripropyl borate, heating at 105 ℃ for 3 hours, placing in 700W microwave treatment at 75 ℃ for 2 hours, centrifuging, and drying to obtain an inorganic compound; adding 1.2 parts of sodium lauryl sulfonate into 100 parts of 0.08wt% acetic acid aqueous solution, uniformly mixing, adding 20 parts of urea, stirring at 28 ℃ and 150rpm for 30min, adding 80 parts of n-propyl trimethoxy silane, and continuously stirring for 35min to obtain SiO2Sol; adding 3.5 parts of inorganic compound and 1 part of silicon nitride into the SiO2Stirring the sol for 2.5h at 28 ℃ and 150rpm, standing for 8h, centrifuging and drying to obtain the heat-insulating filler. The heat insulation performance of the waterproof coating obtained in example 8 is evaluated according to the standard GB/T17371-.
Test example 1
The silane concrete paint is permeable paint, and the waterproof paint has certain solidifying and filming performance. The water absorption ratio is required to be tested according to JG/T337 and 2011 permeable coating for protecting a concrete structure, the carbonization depth ratio is required to be tested according to JG/T335 and 2011 film-forming coating for protecting a concrete structure, the waterproof coating in the embodiments 1-6 is coated on a concrete sample according to requirements, a test sample is obtained to be subjected to related performance test, the size of the concrete sample is 100mm multiplied by 100mm, and the thickness of the coating coated on the surface of the concrete sample is 2 mm.
TABLE 1 correlation of Performance tests
Carbonization depth ratio/%) Water absorption ratio (general Environment)/%
Example 1 5.1 3.1
Example 2 15.5 11.3
Example 3 6.8 5.7
Example 4 7.3 6.5
Example 5 13.2 9.8
Example 6 15.0 10.4
Test example 2
The weather resistance of the waterproof coatings of the examples 1-6 is tested by referring to GB/T1865-.
TABLE 2 weather resistance test results
Powdering grade Foaming rating Grade of exfoliation
Example 1 0 0（S0） 0（S0）
Example 2 3 2（S3） 2（S2）
Example 5 3 3（S3） 2（S3）
Example 6 4 4（S4） 3（S3）
The organosilicon paint has high permeability, and can hydrolyze to obtain high-activity silicon hydroxyl group by silane bond, and condense with concrete surface hydroxyl group to form hydrophobicThe coating film has low reaction activity and high air permeability, and cannot obstruct the corrosion of atmospheric pollutants on concrete. Example 6 after adding photosensitive resin to the silicone, the permeability and the consolidation film forming ability of the silicone and the silicone are combined, and the coating adhesion and the waterproof and gas-proof protective effects are improved. However, the coating is compact, so that the moisture of the concrete is not easy to discharge, the bubbling phenomenon occurs, or the atmospheric pollutants can corrode the concrete while part of the moisture is discharged, and the protection effect is not enough. Example 2 addition of TiO on the basis thereof2Modification of organic silicon by particles, TiO2The particles have ultraviolet shielding performance, the weather resistance of the concrete is improved to a certain extent, the foaming is relatively reduced, the hydrophobicity and the air tightness of the coating are reduced, and the concrete is still easy to corrode. Example 5 use of TiO in addition to example 22Mixing the particles with EDOT to prepare PEDOT self-assembled deposit grown on TiO2A surface. Asymmetric amphiphilic particles are not formed, the film forming property is improved, the waterproofness and the air tightness are improved, but the self-driven directional air guide and water guide effect cannot be realized, the protection effect is not obviously improved, the foaming is easier, and the area of each peeling part is larger on average.
Examples 3 and 4 in example 5, a surface active modifier was selected for TiO2The particles are modified. TiO modified by surface active modifier sodium dodecyl benzene sulfonate2The volume of the particle space is increased, the density is reduced, and the particle space floats on the liquid surface of the carbon tetrabromide; the sodium dodecyl sulfate has high HLB value and strong hydrophilicity, and modified TiO is added2The hydrophilic functional group of the particle is also beneficial to modifying TiO2The particles float at the delamination interface. EDOT is polymerized to generate PEDOT, and the PEDOT is downwards deposited on a layered interface and modified TiO2The upper surface of the particle self-assembles into a shell, generating the asymmetric amphiphilic microparticle. The amphiphilic particles are easy to aggregate to form firework-like clusters, the cluster structure is outward from the side of titanium dioxide, inward from the side of PEDOT, and the hydrophilicity is improved. Under the irradiation of ultraviolet light, the catalytic titanium dioxide provides kinetic energy for the amphiphilic particles to do self-propelling movement, so that cluster particles are dispersed. Under the irradiation of ultraviolet light, the curing and film forming of the coating also occur simultaneously. The closer to the surface of the film, the smaller the cluster degree, the more uniform the particle distribution, the better the film forming property and the hydrophobicityThe higher the water content is, the more dendritic gradient structure is formed, the self-driven directional air guide and water guide can be realized, the weather resistance is improved, and the foaming is reduced. EXAMPLE 1 sodium dodecylbenzenesulfonate and sodium dodecylsulfate were used together with p-TiO2The particles are modified, and the two have synergistic effect, so that the prepared amphiphilic particles have better asymmetric effect and better particle dispersion effect under ultraviolet irradiation. And due to the amphiphilic particles TiO2The difference between the hydrophilic and hydrophobic effects of the side and the PEDOT side is increased, and the cluster structure has stronger hydrophilicity, so that the self-driven directional air guide and water guide effects in the use process of the coating are improved.

Claims (1)

1. The waterproof coating is characterized by comprising the following components in parts by weight: 30-50 parts of modified silane, 12-20 parts of photosensitive resin, 15-20 parts of tetrahydrofuran and 3-8 parts of heat insulation filler;
the modified silane is prepared by the following method:
s1, adding silane monomers into an organic solvent A according to the weight ratio of (1-3) to (4-7), and stirring and dispersing at 200rpm for 30-60min by 150-;
s2, under the dark condition, adding the amphiphilic particles into the organic solvent A according to the material-liquid ratio (1-3) g (15-30) mL, and carrying out ultrasonic-assisted dispersion at 25-40kHz and 200-400W for 30-60min to obtain a particle dispersion liquid;
s3, under the dark condition, mixing the organic silicon solution and the particle dispersion liquid according to the weight ratio of (6-10) to (1-2), and stirring at the speed of 600rpm of 300-;
the preparation method of the amphiphilic particles comprises the following steps:
K1. modified TiO2The particles are added into carbon tetrabromide at 90-95 ℃ according to the material-liquid ratio of 1g (20-30) mL, and are subjected to ultrasonic dispersion for 30-60min at 100-300W and 30-50kHz to obtain modified TiO2Floating liquid on the particles;
K2. adding EDOT into water with the temperature of 90-95 ℃ according to the material-liquid ratio of 1 (30-50), and ultrasonically dispersing for 20-30min at 100-300W and 30-50kHz to obtain EDOT suspension;
K3. adding EDOT suspension into the modified TiO obtained in the step of K1 according to the weight ratio of 1 (3-5)2Particle floating liquidObtaining a mixed solution;
K4. keeping the temperature at 90-95 deg.C, adding Na (20-25): (1-2) by weight ratio into the mixed solution2S2O8And FeCl3In which Na is2S2O8The material-liquid ratio of the mixed solution is 1g (300-400) mL, the mixture is stirred for 1-2min at the rotation speed of 900rpm of 700-400-;
K5. filtering the reaction mixture while the reaction mixture is hot, and sequentially carrying out alcohol washing, water washing and drying to obtain amphiphilic particles;
the modified TiO2The preparation method of the particles comprises the following steps:
t1, dissolving tetrabutyl titanate in absolute ethyl alcohol according to the weight ratio of 1 (3-6) to obtain a solution A;
t2, dissolving a surface active modifier in a 10-14 wt% acetic acid aqueous solution according to a feed-liquid ratio (1-2) g:1000mL to obtain a solution B;
t3, stirring the solution A at the rotation speed of 100-;
t4, placing the reactant in a muffle furnace, heating to 400-600 ℃ at the heating rate of 5-6 ℃/min, roasting for 3-5h, and naturally cooling to room temperature to obtain the modified TiO2A particle;
the silane monomer is selected from at least one of methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane and hexadecyltrimethoxysilane; the organic solvent A is selected from any one of n-butanol, tetrahydrofuran, acetone and butyl acetate; the surface active modifier is selected from at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, monolauryl phosphate and disodium lauryl sulfosuccinate monoester;
the preparation method of the heat insulation filler comprises the following steps:
adding 2-5 parts by weight of aluminum nitrate into 15-30 parts by weight of 80-90wt% ethanol aqueous solution, uniformly mixing, adding 1-3 parts by weight of cerium nitrate and 5-8 parts by weight of tripropyl borate, heating at 90-110 ℃ for 2-4h, placing in 600-800W and 70-80 ℃ for microwave treatment for 1-3h, centrifuging and drying to obtain an inorganic compound; adding 1-2 parts of sodium lauryl sulfonate into 120 parts of 0.05-0.1wt% acetic acid aqueous solution of 100-2Sol; adding 3-5 parts of inorganic compound and 1-2 parts of silicon nitride into the SiO2Stirring the sol for 2 to 3 hours at the temperature of between 25 and 30 ℃ and at the speed of between 100 and 200rpm, standing the sol for 5 to 10 hours, centrifuging the sol and drying the sol to obtain the heat insulation filler;
the photosensitive resin comprises the following components in parts by weight: 20-40 parts of epoxy acrylate resin, 20-30 parts of butyl acrylate and 1-3 parts of bibenzoyl.
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