CN112126284B - Waterproof heat-insulating coating for external wall and preparation method thereof - Google Patents
Waterproof heat-insulating coating for external wall and preparation method thereof Download PDFInfo
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- CN112126284B CN112126284B CN202010986651.8A CN202010986651A CN112126284B CN 112126284 B CN112126284 B CN 112126284B CN 202010986651 A CN202010986651 A CN 202010986651A CN 112126284 B CN112126284 B CN 112126284B
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- 235000012424 soybean oil Nutrition 0.000 claims abstract description 13
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- 230000032683 aging Effects 0.000 claims description 9
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- 239000004005 microsphere Substances 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- -1 dodecyl alcohol ester Chemical class 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
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- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
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- 239000000463 material Substances 0.000 claims 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- AAOVKJBEBIDNHE-UHFFFAOYSA-N diazepam Chemical compound N=1CC(=O)N(C)C2=CC=C(Cl)C=C2C=1C1=CC=CC=C1 AAOVKJBEBIDNHE-UHFFFAOYSA-N 0.000 claims 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 241000282414 Homo sapiens Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- 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
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The application relates to an exterior wall waterproof heat-insulation coating and a preparation method thereof, and the exterior wall waterproof heat-insulation coating comprises the following raw materials in parts by weight: 40-60 parts of styrene-acrylic emulsion, 15-20 parts of reinforcing fiber and TiO25-10 parts of modified hollow glass beads, 10-12 parts of silk fibroin solution, 10-14 parts of nano filler, 3-5 parts of epoxidized soybean oil, 2-3 parts of lauryl methacrylate, 3-4 parts of polymethyl triethoxysilane, 1-3 parts of dispersing agent, 0.2-0.5 part of antiseptic bactericide, 1-2 parts of film forming additive and 15-25 parts of water.
Description
Technical Field
The application relates to the technical field of building materials, in particular to an outer wall waterproof heat-insulating coating and a preparation method thereof.
Background
With the development of human beings and the continuous exploitation and utilization of global resources and energy sources, energy conservation and emission reduction become a basic policy of the country, the building energy consumption accounts for about 35-40% of all energy consumption, and the energy consumption of building heating and air conditioning in summer accounts for 50-75% of the building energy consumption, so that for the building industry, the key for ensuring the energy conservation and emission reduction of the building is to reduce the energy consumption brought by air conditioners and central heating.
At present, in order to reduce energy consumption brought by an air conditioner and a heater, a heat-insulating coating is generally coated on the surface of an outer wall to improve the heat-insulating property of the outer wall of a house, the heat-insulating coating generally realizes heat insulation through low heat conductivity coefficient, and the lower the heat conductivity coefficient is, the better the heat-insulating property of the coating is.
However, the outer wall is eroded by rainwater all the year round, so that the heat-insulating coating is required to have strong waterproof performance, if the waterproof performance of the heat-insulating coating is poor, the outer wall can absorb a large amount of moisture, the outer wall is in a humid environment for a long time, the phenomena of mildew, strength reduction and the like easily occur, and the service life of the outer wall is shortened.
Disclosure of Invention
In order to enable the heat-insulating coating to have higher waterproof performance and further achieve the effect of prolonging the service life of an outer wall, the application provides the outer wall waterproof heat-insulating coating and a preparation method thereof.
In a first aspect, the application provides an exterior wall waterproof heat-insulating coating, which adopts the following technical scheme:
the waterproof heat-insulating coating for the outer wall comprises the following raw materials in parts by weight: 40-60 parts of styrene-acrylic emulsion, 15-20 parts of reinforcing fiber and TiO25-10 parts of modified hollow glass beads, 10-12 parts of silk fibroin solution, 10-14 parts of nano filler, 3-5 parts of epoxidized soybean oil, 2-3 parts of lauryl methacrylate, 3-4 parts of polymethyl triethoxysilane, 1-3 parts of dispersant, 0.2-0.5 part of antiseptic bactericide, 1-2 parts of film forming auxiliary agent and 15-25 parts of water.
By adopting the technical scheme, the styrene-acrylic emulsion with a specific proportion range is selected as a main film forming substance of the exterior wall waterproof heat-insulation coating. The styrene-acrylic emulsion is obtained by emulsion copolymerization of styrene and acrylate monomers, and has the characteristics of strong adhesive force, transparent adhesive film, water resistance, oil resistance, heat resistance, aging resistance and the like, so that the styrene-acrylic emulsion and water are mixed according to a specific proportion to be used as a main film forming substance, and the external wall heat-insulating coating has the characteristics of good water resistance, good weather resistance, good heat-insulating effect and the like.
The application adopts reinforced fiber and TiO2The modified hollow glass beads, the silk fibroin solution, the nano filler and the styrene-acrylic emulsion are mixed and matched according to a specific proportion range for use, a network structure can be formed in the process of mixing and emulsifying with the styrene-acrylic emulsion, the components fully play a synergistic effect with each other, a good shielding effect is achieved on infrared rays, the heat radiation effect is effectively reduced, various heat transfer modes are inhibited, and therefore the heat insulation performance of the exterior wall waterproof heat insulation coating is improved.
The reinforcing fiber is filled in the outer wall waterproof heat-insulation coating, can be used as a framework, plays a role in supporting and shaping, can inhibit the shrinkage of the outer wall waterproof heat-insulation coating during drying, plays a role in reinforcing, improves the mechanical strength of the outer wall waterproof heat-insulation coating, and reduces the possibility of cracking of the outer wall waterproof heat-insulation coating.
Meanwhile, the nano filler can be adsorbed on the reinforcing fiber to form a coating layer, the coating layer can effectively reduce the heat conductivity coefficient of the outer wall waterproof heat-insulating coating and improve the heat-insulating property of the outer wall waterproof heat-insulating coating, so that the heat-insulating property of the outer wall is improved, the coating layer can play a role in protecting and stress buffering on the reinforcing fiber, the mechanical property of the reinforcing fiber is improved, and the mechanical property of the outer wall waterproof heat-insulating coating is further improved.
TiO2The melting point is higher, the high-temperature resistance is good, the ultraviolet shielding effect is good, the direct irradiation of sunlight can be effectively reflected, and the property is stable; the hollow glass microspheres have the characteristics of small heat conductivity coefficient, high refractive index, good heat insulation performance, environmental protection, no toxicity, high temperature resistance and the like; by TiO2The hollow glass beads are modified and coated on the surfaces of the hollow glass beads, so that the heat insulation performance of the exterior wall waterproof heat-insulation coating can be obviously improved.
Simultaneously, the silk fibroin solution and TiO2The modified hollow glass beads are matched and used according to a specific proportion, so that the surface of the exterior wall waterproof heat-insulating coating is compact, the interior of the exterior wall waterproof heat-insulating coating has a certain loose structure, and the waterproof and heat-insulating properties of the exterior wall waterproof heat-insulating coating are greatly improved.
The utility model provides an outside fine and close surface of outer wall waterproof insulation coating and inside network structure that forms can block the infiltration of hydrone in coordination to improve outer wall waterproof insulation coating's waterproof performance, in addition, this application mixes the collocation through adopting epoxidized soybean oil, dodecyl methacrylate, polymethyl triethoxy silane according to specific ratio and uses and add outer wall waterproof insulation coating, utilized the hydrophobicity of above-mentioned each component, the waterproof performance of outer wall waterproof insulation coating has been improved in coordination, thereby the life of outer wall has been prolonged.
Meanwhile, the dispersant, the anticorrosive bactericide and the film-forming assistant in specific proportions are added into the exterior wall waterproof heat-insulation coating, so that the dispersibility of each component in the coating can be improved, and the compatibility among the components is better; the antiseptic bactericide can effectively reduce the possibility of mildew on the outer wall; the film-forming assistant can promote the fluidity of the styrene-acrylic emulsion and reduce the possibility of agglomeration of the coating.
Preferably, the silk fibroin solution is prepared by the following method:
at the temperature of 70-74 ℃, mixing calcium chloride, water and ethanol, stirring for 3-5 min to obtain a mixed solution, then mixing the silk fiber with the mixed solution, and reacting for 50-70 min to obtain a silk fibroin solution, wherein the weight ratio of the calcium chloride to the water to the ethanol is 1: (9-10): (3-3.5), the weight ratio of the silkworm silk fibers to the mixed solution is 1: (9-11).
By adopting the technical scheme, the calcium chloride, the water and the ethanol in a specific ratio are mixed to obtain a ternary solution, the silk fiber of the silkworm is dissolved by using the ternary solution under a specific reaction condition, the obtained silk fibroin solution is added into the external wall waterproof heat-insulating coating according to a specific ratio, and the heat-insulating property of the external wall waterproof heat-insulating coating is further improved.
Preferably, the TiO is2The modified hollow glass bead is prepared by the following method:
s1: stirring absolute ethyl alcohol, butyl titanate and acetic acid at the temperature of 20-24 ℃ for 5-10 min at the rotating speed of 1300-1500 r/min to obtain a mixed solution, wherein the weight ratio of the absolute ethyl alcohol to the butyl titanate to the acetic acid is (8-10): 1: (2-3);
s2: dropwise adding an ethanol solution with the mass concentration of 20-25% into the mixed solution at a constant speed for 5-8 min, standing and aging at the temperature of 20-23 ℃ to obtain light yellow transparent sol, adding hollow glass beads into the light yellow transparent sol, stirring at the rotating speed of 100-130 r/min for 10-20 min, standing, separating, drying at the temperature of 60-80 ℃ for 1-1.5 h, and calcining at a high temperature for 110-130 min to obtain TiO2Modifying hollow glass beads, wherein the weight ratio of the hollow glass beads to the light yellow transparent sol is 1: (48 to 50).
By adopting the technical scheme, the TiO2The inorganic oxide with the highest refractive index in the pigment and filler at present, and the main component of the hollow glass bead is silicate, wherein the hollow structure leads the thermal conductivity coefficient to be smaller, and the hollow glass bead has the advantages ofHas excellent heat insulating performance, so that TiO is prepared by adopting specific raw materials and according to specific reaction conditions2Coating the hollow glass beads with the composite heat-insulating filler (TiO), and combining reflective heat insulation and barrier heat insulation to obtain the composite heat-insulating filler (TiO) with small heat conductivity coefficient and high near-infrared reflectivity2Modifying hollow glass beads), adding TiO2The modified hollow glass beads are added into the exterior wall waterproof heat-insulating coating according to a specific proportion, so that the heat-insulating property of the coating can be effectively improved.
Preferably, in step S2, the high-temperature calcination temperature is 580 to 700 ℃.
By adopting the technical scheme, the high-temperature calcination temperature is controlled within the specific range, so that the surface of the hollow glass bead is almost completely coated with TiO2Wrapped and wrapped more uniformly. If the high-temperature calcination temperature is lower than the range, the surfaces of the hollow glass microspheres are still smooth, and TiO is2Can not be completely wrapped on the surface of the hollow glass microsphere; because the hollow glass beads are of a hollow structure, if the high-temperature calcination temperature is higher than the range, the surfaces of the hollow glass beads are broken.
Preferably, the reinforcing fibers comprise alumina fibers and aluminum silicate fibers, and the weight ratio of the alumina fibers to the aluminum silicate fibers is 1: (1.0-1.2).
By adopting the technical scheme, the alumina fiber and the aluminum silicate fiber both have good heat-resistant and heat-insulating properties, and the alumina fiber and the aluminum silicate fiber are added into the outer wall waterproof heat-insulating coating according to a specific proportion, can be tightly combined with components such as styrene-acrylic emulsion, nano filler and the like, so that the heat-insulating property of the outer wall waterproof heat-insulating coating is improved, and the mechanical property of the outer wall waterproof heat-insulating coating is improved.
Preferably, the nanofiller comprises nano-SiO2And nano ZnO, nano SiO2And nano ZnO in a weight ratio of 1: (0.8 to 1.2).
By adopting the technical scheme, the nano SiO2Has the advantages of high heat resistance value, high strength and the like; the nano ZnO has small grain diameter, large specific surface area and small sizeStress, surface and interface effects, and the like, and therefore has strong capability of scattering and absorbing ultraviolet rays. Mixing nano SiO2The nano ZnO and the nano ZnO are mixed and matched according to a specific proportion for use, and the nano ZnO are applied to the outer wall waterproof heat-insulating coating, so that the coating has the effects of shielding ultraviolet light and absorbing infrared light, the purposes of ultraviolet aging resistance and heat aging resistance are achieved, and the heat-insulating property of the coating is obviously improved.
Furthermore, nano SiO2The nano ZnO is mixed and matched with the nano ZnO according to a specific proportion for use, so that the coating has the effects of resisting bacteria, preventing mildew and decomposing various harmful substances such as formaldehyde and the like; simultaneous nano SiO2And nano ZnO can be used as a reinforcing agent to synergistically improve the waterproof performance and the mechanical property of the coating.
Preferably, the nano ZnO is modified by the following method:
dispersing nano ZnO, a dispersing agent, a silane coupling agent and water at the temperature of 20-24 ℃ for 15-20 min at the rotating speed of 1300-1400 r/min, adjusting the pH value to 8.5-9.5 by using a pH adjusting agent, and then performing ultrasonic dispersion for 25-30 min to obtain modified nano ZnO, wherein the weight ratio of the nano ZnO to the dispersing agent to the silane coupling agent to the water is (1.8-2.2): (0.18-0.22): (0.45-0.55): (95-105).
By adopting the technical scheme, the specific dispersing agent and the silane coupling agent are selected, and the nano ZnO is modified according to the specific proportion, so that the dispersibility of the nano ZnO in the coating is improved, and the compatibility between the nano filler and the styrene-acrylic emulsion is improved, so that the compactness of the coating is improved, and the coating has stronger water resistance, stability and aging resistance.
The dispersing agent SK-5040 is selected as the dispersing agent, the using amount of the dispersing agent is controlled within a specific proportion range, the dispersibility of the nano ZnO can be effectively improved, after the surface of the nano ZnO reaches saturated adsorption, macromolecular chains in the dispersing agent can be mutually wound, the stability of the nano ZnO is reduced, the modification effect of the nano ZnO is influenced, and meanwhile, the cost is increased.
According to the preparation method, the silane coupling agent KH560 is selected as the silane coupling agent, the dosage of the silane coupling agent is controlled within a specific proportion range, and the nano ZnO is modified, so that the modified nano ZnO has good compatibility in the coating. If the dosage of the silane coupling agent is less, the silane coupling agent cannot fully act with the nano ZnO, so that the nano ZnO generates the phenomena of agglomeration, flocculation sedimentation and the like due to the self special nano effect to influence the modification effect; however, if the amount of the silane coupling agent is high, the macromolecular chains in the silane coupling agent are intertwined with each other, but rather, part of the nano ZnO is aggregated into a group, and the molecular chains cannot be stretched, which also affects the modification effect.
Preferably, the dispersing agent is polyethylene glycol 200 and/or polyethylene glycol 400.
Preferably, the film forming aid is dodecyl alcohol ester and/or polyether glycol laurate.
By adopting the technical scheme, the polyethylene glycol 200 and/or the polyethylene glycol 400 are/is used as a dispersing agent, the dodecyl alcohol ester and/or the polyether glycol dodecanoate are/is used as a film forming additive and added into the exterior wall waterproof heat-insulating coating according to a specific proportion range, the compatibility among the components in the coating can be improved, the flowing property of the styrene-acrylic emulsion is promoted, and the possibility of coalescence of the coating is reduced.
In a second aspect, the application provides a preparation method of an exterior wall waterproof heat-insulating coating, which comprises the following steps:
i: at the temperature of 20-24 ℃, firstly, mixing and stirring the styrene-acrylic emulsion, the nano filler, the reinforcing fiber and the dispersing agent for 15-25 min at the rotating speed of 1300-1500 r/min, then adding TiO2 modified hollow glass microspheres at the rotating speed of 130-150 r/min, and stirring for 5-10 min to obtain mixed emulsion;
II: and stirring the mixed emulsion, the silk fibroin solution, the epoxidized soybean oil, the dodecyl methacrylate, the polymethyltriethoxysilane, the anticorrosive bactericide and water at the rotation speed of 150-200 r/min for 20-30 min at the temperature of 20-24 ℃, finally adding the film-forming assistant, and continuously stirring for 5-10 min to obtain the outer wall waterproof heat-insulating coating.
By adopting the technical scheme, firstly, the styrene-acrylic emulsion, the nano-filler, the reinforcing fiber and the dispersing agent are mixed at high speed at a specific temperature and a specific rotating speed, so that the nano-filler and the reinforcing fiber are fully dispersed in the styrene-acrylic emulsion, then the mixture is converted to be at low speed, TiO2 is added to modify the hollow glass beads, and the mixture is continuously mixed, so that all the components are fully combined to obtain mixed emulsion; then, continuously mixing the silk fibroin solution, epoxidized soybean oil, lauryl methacrylate, polymethyl triethoxy silane, the anticorrosive bactericide, water and the mixed emulsion at a specific temperature and a specific rotating speed, and with the help of a film-forming assistant, enabling the prepared exterior wall waterproof heat-insulating coating to have high waterproof performance, heat-insulating performance and mechanical performance.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the styrene-acrylic emulsion is used as a main film forming substance and is assisted by other components, so that the waterproof and heat-insulating coating for the outer wall has high waterproof property and heat-insulating property;
2. the external wall waterproof heat-insulation coating contains the reinforcing fibers and is matched with the nano filler for use, so that the mechanical property and weather resistance of the external wall waterproof heat-insulation coating are improved, and the service life of the coating is prolonged;
3. the preparation method of the exterior wall waterproof heat-insulating coating improves the compatibility of the components in the coating, and has the advantages of simple process and good application prospect.
Detailed Description
The present application will be described in further detail with reference to examples.
In the following preparations, examples and comparative examples:
polyethylene glycol 200 was purchased from Haian petrochemical plants of Jiangsu province;
polyethylene glycol 400 was purchased from Haian petrochemical plants of Jiangsu province;
dodecyl methacrylate was purchased from Shanghai Zhengshiji Co., Ltd;
polymethyl triethoxy silane was purchased from Hangzhou silicon chemical Co., Ltd;
the dodecanol ester was purchased from denland lan hai chemical company;
the polyether polyol dodecanoate is purchased from Haian petrochemical company, Inc. of Jiangsu province;
the antiseptic bactericide is purchased from Dongguan Bo high chemical industry Co.
Preparation example 1
The silk fibroin solution is prepared by the following method:
mixing 10g of calcium chloride, 90g of water and 30g of ethanol at 70 ℃, stirring for 3min to obtain a mixed solution, then mixing 10g of silk fiber with 90g of the mixed solution, and reacting for 50min to obtain a silk fibroin solution.
Preparation example 2
The silk fibroin solution is prepared by the following method:
mixing 10g of calcium chloride, 95g of water and 32.5g of ethanol at 72 ℃, stirring for 4min to obtain a mixed solution, then mixing 10g of silkworm silk fiber with 100g of the mixed solution, and reacting for 60min to obtain the silk fibroin solution.
Preparation example 3
The silk fibroin solution is prepared by the following method:
mixing 10g of calcium chloride, 100g of water and 35g of ethanol at 74 ℃, stirring for 5min to obtain a mixed solution, then mixing 10g of silkworm silk fiber with 110g of the mixed solution, and reacting for 70min to obtain a silk fibroin solution.
Preparation example 4
TiO2The modified hollow glass bead is prepared by the following method:
s1: stirring 80g of absolute ethyl alcohol, 10g of butyl titanate and 20g of acetic acid at the rotation speed of 1300r/min for 5min at the temperature of 20 ℃ to obtain a mixed solution;
s2: dropwise adding an ethanol solution with the mass concentration of 20% into the mixed solution obtained in the step S1 at a constant speed for 5min, standing and aging at the temperature of 20 ℃ to obtain light yellow transparent sol, adding 10g of hollow glass microspheres into 48g of light yellow transparent sol, stirring at the rotating speed of 100r/min for 10min, standing, separating, drying at the temperature of 60 ℃ for 1h, and calcining at the temperature of 580 ℃ for 110min to obtain TiO2Modifying the hollow glass beads.
Preparation example 5
TiO2The modified hollow glass bead is prepared by the following method:
s1: stirring 90g of absolute ethyl alcohol, 10g of butyl titanate and 25g of acetic acid at the temperature of 22 ℃ for 7.5min at the rotating speed of 1400r/min to obtain a mixed solution;
s2: dropwise adding an ethanol solution with the mass concentration of 22.5% into the mixed solution obtained in the step S1 at a constant speed for 6.5min, standing and aging at 21.5 ℃ to obtain light yellow transparent sol, adding 10g of hollow glass microspheres into 49g of light yellow transparent sol, stirring at a rotating speed of 125r/min for 15min, standing, separating, drying at 70 ℃ for 1.25h, and calcining at 640 ℃ for 120min to obtain TiO2Modifying the hollow glass beads.
Preparation example 6
TiO2The modified hollow glass bead is prepared by the following method:
s1: stirring 100g of absolute ethyl alcohol, 10g of butyl titanate and 30g of acetic acid at the temperature of 24 ℃ for 10min at the rotating speed of 1500r/min to obtain a mixed solution;
s2: dropwise adding an ethanol solution with the mass concentration of 25% into the mixed solution obtained in the step S1 at a constant speed for 8min, standing and aging at the temperature of 23 ℃ to obtain light yellow transparent sol, adding 10g of hollow glass microspheres into 50g of light yellow transparent sol, stirring at the rotating speed of 130r/min for 20min, standing, separating, drying at the temperature of 80 ℃ for 1.5h, and calcining at the temperature of 700 ℃ for 130min to obtain TiO2Modifying the hollow glass beads.
Example 1
A preparation method of the exterior wall waterproof heat-insulating coating comprises the following steps:
i: at the temperature of 20 ℃, 40g of styrene-acrylic emulsion and 10g of nano filler (nano SiO) are firstly added2 5.56g, 4.44g of nano ZnO), 20g of reinforcing fiber (10 g of alumina fiber and 10g of aluminum silicate fiber) and 1g of dispersant (polyethylene glycol 200) at the rotating speed of 1300r/minThen, the mixture was stirred for 15min, and 5g of the TiO prepared in preparation example 4 was added at a rotation speed of 130r/min2Modifying the hollow glass beads, and stirring for 5min to obtain a mixed emulsion;
II: and stirring the mixed emulsion, 12g of the silk fibroin solution prepared in the preparation example 1, 5g of epoxidized soybean oil, 2g of lauryl methacrylate, 4g of polymethyl triethoxysilane, 0.5g of an anticorrosive bactericide and 25g of water at the temperature of 20 ℃ for 20min at the rotating speed of 150r/min, finally adding 1g of a film-forming aid (dodecyl alcohol ester), and continuously stirring for 5min to obtain the exterior wall waterproof heat-insulating coating.
Example 2
A preparation method of the exterior wall waterproof heat-insulating coating comprises the following steps:
i: 50g of styrene-acrylic emulsion and 12g of nano-filler (nano SiO) are firstly added at the temperature of 22 DEG C25.45g of nano ZnO, 6.55g of nano ZnO), 17.5g of reinforcing fiber (7.95 g of alumina fiber and 9.55g of aluminum silicate fiber) and 2g of dispersing agent (1 g of polyethylene glycol 200 and 1g of polyethylene glycol 400) are mixed and stirred for 20min at the rotating speed of 1400r/min, and then 7.5g of TiO prepared in preparation example 5 is added at the rotating speed of 140r/min2Modifying the hollow glass beads, and stirring for 7.5min to obtain a mixed emulsion;
II: at the temperature of 22 ℃, stirring the mixed emulsion, 11g of the silk fibroin solution prepared in the preparation example 2, 4g of epoxidized soybean oil, 2.5g of lauryl methacrylate, 3.5g of polymethyl triethoxy silane, 0.35g of an anticorrosive bactericide and 20g of water at the rotating speed of 175 r/min for 25min, finally adding 1.5g of a film-forming assistant (1 g of dodecyl alcohol ester and 0.5g of polyether glycol laurate), and continuously stirring for 7.5min to obtain the waterproof and heat-insulating coating for the exterior wall.
Example 3
A preparation method of the exterior wall waterproof heat-insulating coating comprises the following steps:
i: at the temperature of 24 ℃, 60g of styrene-acrylic emulsion and 14g of nano filler (nano SiO) are firstly added27g of nano ZnO, 7g of nano ZnO), 15g of reinforcing fiber (7.14 g of alumina fiber, 7.86g of aluminum silicate fiber) and 3g of dispersing agent (polyethylene glycol 400) are mixed and stirred for 25min at the rotating speed of 1500r/min, and then 15g of the mixture is stirred at the rotating speed of 15 r/minAt a rotational speed of 0r/min, 10g of the TiO prepared in preparation example 6 were added2Modifying the hollow glass beads, and stirring for 10min to obtain a mixed emulsion;
II: and stirring the mixed emulsion, 10g of the silk fibroin solution prepared in the preparation example 3, 3g of epoxidized soybean oil, 3g of lauryl methacrylate, 3g of polymethyl triethoxysilane, 0.2g of an anticorrosive bactericide and 15g of water at the temperature of 24 ℃ for 30min at the rotating speed of 200r/min, finally adding 2g of a film-forming aid (polyether glycol dodecanoate), and continuously stirring for 10min to obtain the exterior wall waterproof and heat-insulating coating.
Example 4
A preparation method of an exterior wall waterproof heat-insulation coating is different from that of the embodiment 2 in that: the nano ZnO is modified by the following method:
dispersing 1.8g of nano ZnO, 0.18g of dispersing agent SK-5040, 0.45g of silane coupling agent KH560 and 95g of water at the temperature of 20 ℃ for 15min at the rotating speed of 1300r/min, adjusting the pH value to 8.5 by using a pH regulator (sodium carbonate), and then ultrasonically dispersing for 25min to obtain the modified nano ZnO.
Example 5
A preparation method of an exterior wall waterproof heat-insulation coating is different from that of the embodiment 2 in that: the nano ZnO is modified by the following method:
dispersing 2.2g of nano ZnO, 0.22g of dispersing agent SK-5040, 0.55g of silane coupling agent KH560 and 105g of water at the temperature of 24 ℃ for 20min at the rotating speed of 1400r/min, adjusting the pH value to 9.5 by using a pH regulator (sodium carbonate), and then performing ultrasonic dispersion for 30min to obtain the modified nano ZnO.
Comparative example 1
The common exterior wall coating is purchased from Shanghai environmental protection technology Limited, Juhai, Inc., Cathaki No. 8085.
Comparative example 2
The difference from example 2 is that: reinforcing fiber 10g, TiO22g of modified hollow glass beads, 5g of silk fibroin solution, 5g of nano filler, 1g of epoxidized soybean oil, 0.5g of lauryl methacrylate, 2g of polymethyl triethoxy silane, 0.5g of dispersing agent, 0.05g of antiseptic bactericide and 0.5g of film-forming assistant.
Comparative example 3
The difference from example 2 is that: reinforcing fiber 30g, TiO215g of modified hollow glass beads, 15g of silk fibroin solution, 20g of nano filler, 8g of epoxidized soybean oil, 4.5g of lauryl methacrylate, 5.5g of polymethyl triethoxy silane, 4g of dispersing agent, 0.8g of antiseptic bactericide and 2.5g of film-forming assistant.
Performance detection
The exterior wall waterproof heat-insulating coating prepared by the embodiments 1-5 and the comparative examples 1-3 is subjected to waterproof performance, heat-insulating performance and mechanical performance tests, and the detection results are shown in table 1:
and (3) testing the waterproof performance: according to the determination method in GB/T1733 + 1993, the waterproof and heat-insulating coating for the outer wall prepared in the examples 1-5 and the comparative examples 1-3 is coated on a tin plate, the water temperature is adjusted to 47-50 ℃, NaCl with the concentration of 3% is added into the water, the tin plate coated with the coating is completely immersed in salt water, observation is carried out once every 48 hours, and the falling, bubbling or cracking time (d) is recorded;
heat preservation and heat insulation performance: the WNK-200D type flat plate high-temperature thermal conductivity meter of Nanjing Tet electronic technology Limited is adopted to test the thermal conductivity coefficient (W/(m.k)) at 25 ℃ according to the steady state method specified in GB/T17171-2008;
and (3) testing mechanical properties: according to the detection method in GB/T50081-2002, the exterior wall waterproof heat-insulating coatings prepared in the embodiments 1-5 and the comparative examples 1-3 are uniformly coated on the surface of a concrete block, the coating thickness is the same, and the flexural strength (MPa) of the exterior wall is detected for 29 d.
TABLE 1
| Item | Time (d) | Thermal conductivity (W/(m.k)) | Breaking strength (Mpa) |
| Example 1 | 18 | 0.038 | 6.71 |
| Example 2 | 20 | 0.035 | 6.75 |
| Example 3 | 18 | 0.037 | 6.72 |
| Example 4 | 24 | 0.030 | 7.01 |
| Example 5 | 24 | 0.029 | 7.05 |
| Comparative example 1 | 7 | 0.068 | 3.51 |
| Comparative example 2 | 10 | 0.050 | 4.21 |
| Comparative example 3 | 12 | 0.052 | 4.26 |
As can be seen from Table 1, the thermal conductivity of the exterior wall waterproof and heat-insulating coating prepared in the examples 1 to 3 is obviously lower than that of the comparative example 1, the breaking strength is obviously higher than that of the comparative example 1, the exterior wall waterproof and heat-insulating coating prepared in the examples 1 to 5 has the phenomenon of falling off, bubbling or cracking after 18 days, and the exterior wall waterproof and heat-insulating coating prepared in the comparative example 1 has the phenomenon of falling off, bubbling or cracking after 7 days, which indicates that the exterior wall waterproof and heat-insulating coating prepared in the examples 1 to 5 has higher waterproof performance, heat-insulating performance and mechanical performance.
The thermal conductivity of the embodiments 4 to 5 is lower than that of the embodiment 2, the breaking strength is higher than that of the embodiment 2, and the phenomena of falling, bubbling or cracking occur in the exterior wall waterproof thermal insulation coating prepared in the embodiments 4 to 5 at 24 days, which indicates that the waterproof performance, the thermal insulation performance and the mechanical performance of the exterior wall waterproof thermal insulation coating can be obviously improved by modifying the nano ZnO.
The thermal conductivity coefficient of the comparative examples 2-3 is higher than that of the example 2, the flexural strength is lower than that of the example 2, and the phenomena of falling, bubbling or cracking of the exterior wall waterproof heat-insulating coating prepared by the comparative examples 2-3 appear in 10-12 days, which shows that the reinforced fibers and TiO are2The proportions of the modified hollow glass beads, the silk fibroin solution, the nano filler, the epoxidized soybean oil, the lauryl methacrylate, the polymethyltriethoxysilane, the dispersant, the anticorrosive bactericide and the film-forming assistant are too low or too high, so that the waterproof performance, the heat-insulating performance and the mechanical performance of the exterior wall waterproof heat-insulating coating are reduced.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (5)
1. The waterproof heat-insulating coating for the outer wall is characterized by comprising the following raw materials in parts by weight: 40-60 parts of styrene-acrylic emulsion, 15-20 parts of reinforcing fiber and TiO25-10 parts of modified hollow glass beads, 10-12 parts of silk fibroin solution, 10-14 parts of nano filler, 3-5 parts of epoxidized soybean oil, 2-3 parts of lauryl methacrylate, 3-4 parts of polymethyl triethoxysilane, 1-3 parts of dispersant, 0.2-0.5 part of antiseptic bactericide, 1-2 parts of film forming auxiliary agent and 15-25 parts of water, wherein the reinforcing fiber comprises alumina fiber and aluminum silicate fiber, and the weight ratio of the alumina fiber to the aluminum silicate fiber is 1: (1.0-1.2), wherein the nano filler comprises nano SiO2And nano ZnO, nano SiO2And nano ZnO in a weight ratio of 1: (0.8 to 1.2);
the silk fibroin solution is prepared by adopting the following method:
at the temperature of 70-74 ℃, mixing calcium chloride, water and ethanol, stirring for 3-5 min to obtain a mixed solution, then mixing the silk fiber with the mixed solution, and reacting for 50-70 min to obtain a silk fibroin solution, wherein the weight ratio of the calcium chloride to the water to the ethanol is 1: (9-10): (3-3.5), the weight ratio of the silkworm silk fibers to the mixed solution is 1: (9-11);
the TiO is2The modified hollow glass bead is prepared by the following method:
s1: stirring absolute ethyl alcohol, butyl titanate and acetic acid at the temperature of 20-24 ℃ for 5-10 min at the rotating speed of 1300-1500 r/min to obtain a mixed solution, wherein the weight ratio of the absolute ethyl alcohol to the butyl titanate to the acetic acid is (8-10): 1: (2-3);
s2: dropwise adding an ethanol solution with the mass concentration of 20-25% into the mixed solution at a constant speed for 5-8 min, standing and aging at the temperature of 20-23 ℃ to obtain light yellow transparent sol, adding hollow glass beads into the light yellow transparent sol, stirring at the rotating speed of 100-130 r/min for 10-20 min, standing, separating, drying at the temperature of 60-80 ℃ for 1-1.5 h, and calcining at a high temperature for 110-130 min to obtain TiO2Modifying hollow glass microspheres, wherein the weight ratio of the hollow glass microspheres to the light yellow transparent solIs 1: (4.8-5.0);
the nano ZnO is modified by the following method:
dispersing nano ZnO, a dispersing agent, a silane coupling agent and water at the temperature of 20-24 ℃ for 15-20 min at the rotating speed of 1300-1400 r/min, adjusting the pH value to 8.5-9.5 by using a pH adjusting agent, and then performing ultrasonic dispersion for 25-30 min to obtain modified nano ZnO, wherein the weight ratio of the nano ZnO to the dispersing agent to the silane coupling agent to the water is (1.8-2.2): (0.18-0.22): (0.45-0.55): (95-105).
2. The exterior wall waterproof heat-insulating coating material of claim 1, which is characterized in that: in step S2, the temperature of the high-temperature calcination is 580-700 ℃.
3. The exterior wall waterproof heat-insulating coating material of claim 1, which is characterized in that: the dispersing agent is selected from polyethylene glycol 200 and/or polyethylene glycol 400.
4. The exterior wall waterproof heat-insulating coating material of claim 1, which is characterized in that: the film-forming assistant is dodecyl alcohol ester and/or polyether glycol laurate.
5. The preparation method of the exterior wall waterproof and heat-insulating coating as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
i: at the temperature of 20-24 ℃, firstly, mixing and stirring the styrene-acrylic emulsion, the nano filler, the reinforcing fiber and the dispersing agent at the rotating speed of 1300-1500 r/min for 15-25 min, and then adding TiO at the rotating speed of 130-150 r/min2Modifying the hollow glass beads, and stirring for 5-10 min to obtain a mixed emulsion;
II: and stirring the mixed emulsion, the silk fibroin solution, the epoxidized soybean oil, the dodecyl methacrylate, the polymethyltriethoxysilane, the anticorrosive bactericide and water at the rotation speed of 150-200 r/min for 20-30 min at the temperature of 20-24 ℃, finally adding the film-forming assistant, and continuously stirring for 5-10 min to obtain the outer wall waterproof heat-insulating coating.
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