CN115029043A - Energy-saving emission-reducing water-based heat-insulating reflective coating and production process thereof - Google Patents
Energy-saving emission-reducing water-based heat-insulating reflective coating and production process thereof Download PDFInfo
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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
- C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
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- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses an energy-saving emission-reducing water-based heat-insulating reflective coating and a production process thereof, wherein the coating comprises 40-60% of organic silicon modified acrylic emulsion, 8-10% of modified titanium coated hollow ceramic microspheres, 10-15% of rutile titanium dioxide, 10-15% of talcum powder, 5-15% of water and the balance of auxiliary agents in percentage by weight; according to the invention, the barrier heat-insulating material and the reflective heat-insulating material are combined, the obtained coating not only has a good reflection effect on sunlight, but also has an excellent heat transfer barrier effect even when the coating layer is very thin, so that the requirements of energy conservation and emission reduction are met, and the coating has a very high application value.
Description
Technical Field
The invention belongs to the technical field of heat-insulating coatings, and particularly relates to an energy-saving and emission-reducing water-based heat-insulating reflective coating and a production process thereof.
Background
Solar energy is a necessary condition for human survival and life, but strong radiation also brings many problems and inconveniences to human industrial production and daily life. Under the irradiation of sunlight, heat is continuously accumulated on the surface of an irradiated object, so that the surface temperature of the irradiated object is continuously increased, for example, the surface temperature of the irradiated object can reach 70-80 ℃ when the sunlight irradiates on a metal plate in summer. Due to the influence of a heat island effect, the temperature of an urban area of a common city is 3-5 ℃ higher than that of a peripheral area, the temperature of the roof and the surface of the outer wall of a building is increased to cause overhigh temperature of the surrounding environment and the indoor environment, and the electric quantity for air conditioning refrigeration is increased. Statistics show that in the hot afternoon, the once-a-day rise in maximum temperature requires a rise in power supply of around 2%. Meanwhile, more and more iron sheet tops are adopted in the current industrial factory buildings, simple factory buildings or temporary buildings, so that the temperature of the room has to be reduced by adopting an air conditioner or a water spraying mode in hot summer, but the indoor temperature cannot be effectively reduced by adopting the air conditioner under many conditions. Therefore, it is an important research subject to reduce or prevent the temperature rise due to the intense solar radiation by various methods. Since the 70 s, countries such as England America and Japan continue to develop heat-insulating coatings in related fields so as to achieve the purposes of improving the environment, saving energy, improving the safety and the like.
The heat-insulating coating can be classified into a barrier heat-insulating coating, a radiant heat-insulating coating, and a reflective heat-insulating coating based on the difference between the heat-insulating mechanism and the heat-insulating manner. Barrier thermal barrier coatings achieve thermal insulation by a significant resistance to heat transfer. The reflective heat-insulating coating is prepared by selecting proper resin, metal or metal oxide pigment and filler and a production process to obtain a coating with high reflectivity to reflect solar heat to achieve heat insulation. The radiation type heat insulation coating radiates sunlight and heat absorbed by a building into the air in a certain wavelength in a radiation mode, so that a good heat insulation and cooling effect is achieved. The raw materials of the barrier type heat insulation coating are easily obtained, production equipment is simple, investment is low, output is large, construction is convenient, the effect of reducing convection and radiation heat transfer is poor, the coating is thick (the coating generally needs to reach centimeter level and has obvious heat insulation effect), the water absorption rate is high, vibration is not resisted, the coating is easy to fall off, the service life is short, and a waterproof layer and an outer protective layer are usually required to be additionally arranged. The radiant heat insulation coating can radiate absorbed heat in a heat emission mode, and avoids overhigh temperature inside the coating, so that the indoor and outdoor temperature reduction is promoted at the same speed, but the raw materials of the coating are selected rigorously and the sintering process is complex, and the industrial production cannot be realized. The advantages and disadvantages of the reflective thermal insulation coating are respectively as follows: the coating has good adhesion with various base materials, good compatibility with primer intermediate paint, strong weather resistance, obvious heat insulation effect compared with the barrier type heat insulation coating, and irrelevant effect with coating thickness, but the coating can relieve temperature rise, also can heat the surface of a paint film, cannot realize real heat insulation, most of reflective heat insulation coatings are solvent systems, and the current architectural coating is widely used as a water-based coating.
The three types of coatings have advantages and disadvantages, and the application occasions and the obtained effects are different. A coating that is well insulated is often the result of two or more insulation mechanisms acting simultaneously. Therefore, the characteristics of various materials are fully exerted, the advantages and the disadvantages are brought into play, and the development of the composite heat-insulating coating with various heat-insulating mechanisms comprehensively acting represents the development trend of future heat-insulating coatings.
Disclosure of Invention
In view of the above, the invention aims to provide a composite water-based heat insulation coating, which combines a barrier heat insulation material and a reflective heat insulation material, has a good reflection effect on sunlight, has an excellent heat transfer barrier effect even when a coating layer is thin, and meets the requirements of energy conservation and emission reduction.
In order to achieve the above purpose, the technical solution of the present invention is specifically:
an energy-saving emission-reducing water-based heat-insulating reflective coating comprises 40-60% of organic silicon modified acrylic emulsion, 8-10% of modified titanium coated hollow ceramic microspheres, 10-15% of rutile titanium white, 10-15% of talcum powder, 5-15% of water and the balance of auxiliaries in percentage by weight.
The organic silicon modified acrylic emulsion is formed by polymerizing an organic silicon monomer containing an unsaturated bond and acrylic acid, wherein the organic silicon monomer is a vinyl-terminated siloxane oligomer, Mn is 1600-2200, a grafted and modified acrylic main chain is a copolymer of methyl methacrylate and butyl acrylate, the grafting rate of organic silicon is 20-30%, the solid content of the emulsion is 40-60%, and the silicon content is 35-50%.
Further, in the technical scheme, the auxiliary agent comprises 1-5% of a film forming auxiliary agent, 0.5-5% of a dispersing agent, 0.5-5% of an anti-flash rust inhibitor, 0.1-5% of a flatting agent and 0.1-5% of a defoaming agent in percentage by weight.
Furthermore, in the above technical solution, the film forming assistant is dodecyl alcohol ester, the dispersant is siloxane, the flash rust inhibitor is organic zinc chelate, the defoamer is aqueous silicone, and the leveling agent is dimethyl siloxane.
Further, in the above technical scheme, the structure of the modified titanium-coated hollow ceramic bead is as follows: the surface of the hollow ceramic microsphere is sequentially wrapped with a titanium dioxide layer and a fluorosilicone layer. Further, the fluorosilicone is perfluorooctyltriethoxysilane.
Further, in the technical scheme, the particle size of the modified titanium-coated hollow ceramic microspheres is 10-100 um.
Further, in the above technical scheme, the preparation of the modified titanium-coated hollow ceramic bead comprises the following steps:
step 2, placing the pretreated hollow ceramic microspheres in a titanium sulfate solution for sol-gel reaction, and sintering the hollow ceramic microspheres after the reaction is finished to obtain titanium-coated hollow ceramic microspheres;
and 3, placing the titanium-coated hollow ceramic microspheres in a carbon tetrachloride solution of fluorosilicone for reaction, and drying after the reaction is finished.
Further, the pretreatment in step 1 is specifically: placing the hollow ceramic micro-beads in Ca (OH) 2 Etching in saturated aqueous solution.
Furthermore, the sintering temperature in the step 2 is 700-1200 ℃.
Furthermore, the concentration of the titanium sulfate solution is 10-40 wt%, the concentration of the fluorosilicone carbon tetrachloride solution is 10-15 wt%, and the reaction temperature in the step 3 is 30-50 ℃.
The invention further provides a preparation method of the energy-saving emission-reducing water-based heat-insulating reflective coating, which comprises the following steps: mixing the organic silicon modified acrylic emulsion, rutile type titanium white, talcum powder and an auxiliary agent in proportion, grinding and dispersing, adding the modified titanium coated hollow ceramic microspheres in batches for dispersing, and finally adding water to adjust the viscosity of the coating.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, the titanium-coated hollow ceramic microspheres are used as the filler, so that the infrared-light-reflecting ceramic composite material has a good infrared-light reflecting effect, is low in heat conductivity coefficient and has a good reflecting and heat-insulating effect;
2) the fluorosilicone modified titanium-coated hollow ceramic microspheres have strong hydrophobicity, can be stably dispersed in organic silicon modified acrylic emulsion (silicone-acrylic emulsion), can remarkably reduce the addition amount of the filler by 8-10% on the premise of ensuring the excellent reflective insulation effect of the coating, and is far lower than the addition amount (usually 60-80%) of the functional filler in the reflective insulation coating on the market, so that the paint film is prevented from being pulverized and dropped off quickly, and the weather resistance and the validity period of the paint are greatly improved;
3) the coating system simultaneously contains rutile titanium white and talcum powder, and the rutile titanium white is a white pigment filler and can reflect infrared light in sunlight so as to further improve the reflection performance of the coating; the talcum powder has large oil absorption, can adjust the viscosity of the coating, provides convenience for settlement prevention and construction, and can improve the wear resistance of the coating;
4) the titanium-coated hollow ceramic microspheres have abundant active hydroxyl groups on the surfaces, and the fluorosilicone can generate the active hydroxyl groups under the hydrolysis condition, and the active hydroxyl groups and the fluorosilicone are dehydrated and condensed to form stable chemical bonds, so that the modified titanium-coated hollow ceramic microspheres have extremely stable structures and cannot be damaged in the grinding and dispersing process of paint preparation;
5) the coating can achieve stable heat insulation and reflection effects when the thickness of the coating is only 100um, and if the temperature is increased by 1 ℃ and the power supply is increased by about 2%, the coating (with the thickness of 100um) can save 45.2% of power when the coating is coated on the outer surface of an object, so that the coating has a very high application value.
Drawings
FIG. 1 is a comparison of the surface topography of titanium-coated hollow ceramic microspheres (right) and uncoated hollow ceramic microspheres (left);
FIG. 2 is a structural diagram of the surface morphology of the hollow ceramic microsphere coated with titanium after being modified by perfluorooctyl triethoxysilane.
Detailed Description
In order that the invention may be better understood, reference will now be made to the following examples which illustrate the invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
The composition of the water-based heat-insulating reflective coating in the embodiment is specifically as follows: 45% of organosilicon modified acrylic emulsion (DICwas-1070), 9.5% of modified titanium-coated hollow ceramic microspheres, 12% of rutile titanium dioxide, 13% of talcum powder, 2% of film-forming assistant (American Issman texanol), 1% of dispersant (Germany Bike chemical DISPERBYK-2010), 2% of flash rust inhibitor (Nippon modest AKN-0660), 1% of defoamer (Germany Bike chemical BYK-024), 2% of leveling agent and 12.5% of deionized water in percentage by weight.
The preparation process comprises the following steps:
(1) preparation of modified titanium-coated hollow ceramic microspheres
Ceramic Microspheres (3M company Ceramic Microspheres series w210) with a particle size of about 20 μ M were poured into Ca (OH) 2 Slowly stirring in saturated water solution for 12h, filtering and drying; then the pretreated and dried hollow ceramic micro-beads are added with 30 wt% of Ti (SO) 4 ) 2 Stirring and heating in water solution (the mass ratio of the micro-beads to the solution is 1:100) to carry out sol-gel reaction, drying the micro-beads after the reaction, and sintering at the high temperature of 800 ℃ for 12 hours to obtain the product with the outer surface coated by titanium dioxideThe hollow ceramic microbeads of (1).
The hollow ceramic microspheres coated with titanium are put into 12 wt% of anhydrous carbon tetrachloride solution of perfluorooctyl triethoxysilane (the mass ratio of the microspheres to the solution is 1:100) in batches, slowly stirred for 12 hours at 45 ℃, filtered and dried to obtain the modified hollow ceramic microspheres coated with titanium.
(2) Preparation of the coating
Adding the organic silicon modified acrylic emulsion, rutile type titanium dioxide, talcum powder and auxiliary agent into a horizontal sand mill according to the proportion for grinding and dispersing, slowly dispersing the batch modified titanium coated hollow ceramic microspheres until no floating object exists on the surface, adding deionized water to adjust the viscosity of the coating, and finally subpackaging and sealing.
Surface morphology characterization is carried out on the prepared titanium-coated hollow ceramic microspheres and the titanium-coated hollow ceramic microspheres modified by the perfluorooctyl triethoxysilane by adopting SEM, and the surface morphology is specifically shown in figures 1 and 2: the surface of the uncoated nano hollow ceramic microsphere is provided with micro holes, and most of the surface of the completely coated hollow ceramic microsphere is smooth and flat; and modified TiO 2 The surface of the coated hollow ceramic microsphere is obviously coated by perfluorooctyl triethoxysilane.
Coating the paint on a substrate, enabling the thickness of the dried paint to be about 100 mu m, and detecting the heat insulation effect according to GB/T25261-2018 reflective heat insulation paint for buildings, wherein the detection results are shown in the following table:
example 2
The composition of the water-based heat-insulating reflective coating in the embodiment is specifically as follows: 50% of organosilicon modified acrylic emulsion (DICwas-1070), 9% of modified titanium-coated hollow ceramic microspheres, 11% of rutile titanium dioxide, 11% of talcum powder, 2% of film-forming assistant (American Issman texanol), 1% of dispersant (German Bike chemical DISPERBYK-2010), 2% of flash rust inhibitor (Nipponde moded AKN-0660), 1% of defoamer (German Bike chemical BYK-024), 2% of leveling agent and 11% of deionized water in percentage by weight.
The preparation process differs from that of example 1 in that Ti (SO) 4 ) 2 The concentration of the aqueous solution is 20 wt%, the sintering temperature is 100 ℃, the concentration of the anhydrous carbon tetrachloride solution of the perfluorooctyl triethoxysilane is 10%, and the modification temperature is 30 ℃.
Comparative example 1
The difference between this example and example 1 is that only the surfaces of the hollow ceramic beads were coated with titanium dioxide, and the other examples are the same as example 1.
The coating prepared in this example was very poor in stability relative to example 1, as shown in: after a period of time of placement, the titanium-coated hollow nano ceramic microspheres can float on the surface of the coating system again; and as the micro-beads are of a hollow structure, the micro-beads are broken due to re-stirring and dispersion, so that the heat insulation effect of the coating is remarkably reduced.
Comparative example 2
In contrast to comparative example 1, the coating system of this example additionally contains 2% perfluorooctyltriethoxysilane, all otherwise identical to comparative example 1.
The stability of the coating prepared in this example was slightly improved relative to comparative example 1, but was still significantly worse than in example 1.
The raw materials listed in the invention, the values of the upper limit and the lower limit and the interval of the raw materials, and the values of the upper limit and the lower limit and the interval of the process parameters can all realize the invention, and the examples are not listed.
In addition, the stability of the ceramic beads modified with Perfluorooctyltriethoxysilane (PFOES) is optimal relative to other fluorosilicones, and the heat insulation effect is optimal under the condition of the same amount of the hollow ceramic beads. The reason for this analysis is: PFOES can generate 3 active hydroxyls under the hydrolysis condition, the combination of the rest titanium-coated hollow ceramic microspheres is stronger, and the PFOES contains a high F element, has strong hydrophobic effect and can be better and more stably dispersed in an aqueous resin system.
The above description is of the preferred embodiment of the present invention and should not be taken as limiting the scope of the invention, but rather, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The energy-saving emission-reducing water-based heat-insulating reflective coating is characterized by comprising 40-60% of organic silicon modified acrylic emulsion, 8-10% of modified titanium coated hollow ceramic microspheres, 10-15% of rutile titanium dioxide, 10-15% of talcum powder, 5-15% of water and the balance of auxiliary agents in percentage by weight.
2. The energy-saving emission-reducing water-based heat-insulating reflective coating as claimed in claim 1, wherein the auxiliary comprises 1-5% of a film-forming auxiliary, 0.5-5% of a dispersant, 0.5-5% of an anti-flash rust inhibitor, 0.1-5% of a leveling agent and 0.1-5% of a defoaming agent in percentage by weight.
3. The energy-saving emission-reducing water-based heat-insulating reflective coating as claimed in claim 2, wherein the film-forming assistant is a dodecyl ester, the dispersant is a siloxane, the flash rust inhibitor is an organic zinc chelate, the defoamer is an aqueous organosilicon, and the leveling agent is a dimethyl siloxane.
4. The energy-saving emission-reducing water-based heat-insulating reflective coating as claimed in claim 1, wherein the structure of the modified titanium-coated hollow ceramic microspheres is as follows: the surface of the hollow ceramic microsphere is sequentially wrapped with a titanium dioxide layer and a fluorosilicone layer.
5. The energy-saving emission-reducing water-based heat-insulating reflective coating as claimed in claim 4, wherein the fluorosilicone is perfluorooctyltriethoxysilane.
6. The energy-saving emission-reducing water-based heat-insulating reflective coating as claimed in claim 1, wherein the particle size of the modified titanium-coated hollow ceramic micro-beads is 10-100 um.
7. The energy-saving emission-reducing water-based heat-insulating reflective coating as claimed in claim 4, wherein the preparation of the modified titanium-coated hollow ceramic microbeads comprises the following steps:
step 1, pretreating hollow ceramic microspheres to improve the surface roughness of the hollow ceramic microspheres;
step 2, placing the pretreated hollow ceramic microspheres in a titanium sulfate solution for sol-gel reaction, and sintering the hollow ceramic microspheres after the reaction is finished to obtain titanium-coated hollow ceramic microspheres;
and 3, placing the titanium-coated hollow ceramic microspheres in a carbon tetrachloride solution of fluorosilicone for reaction, and drying after the reaction is finished.
8. The energy-saving emission-reducing water-based heat-insulating reflective coating as claimed in claim 7, wherein the pretreatment method in step 1 is as follows: placing the hollow ceramic micro-beads in Ca (OH) 2 Etching in saturated aqueous solution.
9. The energy-saving emission-reducing water-based heat-insulating reflective coating as claimed in claim 7, wherein the sintering temperature in step 2 is 700-1200 ℃.
10. A method for preparing the energy-saving emission-reducing water-based heat-insulating reflective coating as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps: mixing the organic silicon modified acrylic emulsion, rutile type titanium white, talcum powder and an auxiliary agent in proportion, grinding and dispersing, adding the modified titanium coated hollow ceramic microspheres in batches for dispersing, and finally adding water to adjust the viscosity of the coating.
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