CN115011195A - Water-based heat-insulation reflective composite coating with low heat conductivity coefficient and preparation process thereof - Google Patents
Water-based heat-insulation reflective composite coating with low heat conductivity coefficient and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a water-based heat-insulating reflective composite coating with low heat conductivity coefficient and a preparation process thereof, wherein the water-based heat-insulating reflective composite coating comprises the following components in parts by weight: 40-60% of organic silicon modified acrylic emulsion, 6-10% of modified ceramic coated hollow glass microspheres, 10-15% of titanium dioxide, 10-15% of talcum powder, 5-15% of deionized water and the balance of auxiliary agent in percentage by weight; the hollow glass bead coated with the modified ceramic has the structure that the surface of the hollow glass bead is sequentially coated with a ceramic layer and a fluorosilicone layer. The coating provided by the invention can realize excellent heat insulation effect on the premise of extremely small addition amount of the powder filler, and has strong integral weather resistance and long actual service life, so that the coating has good application prospect.
Description
Technical Field
The invention belongs to the technical field of heat-insulating coatings, and particularly relates to a water-based heat-insulating reflective composite coating with a low heat conductivity coefficient and a preparation process thereof.
Background
Solar energy is a necessary condition for human survival and life, but strong radiation can continuously raise the surface temperature of an object, which brings many problems and inconveniences to human industrial production and daily life, so that the application of various methods to reduce or prevent the temperature rise caused by strong radiation of sunlight is an important research subject. Among them, the thermal barrier coating is one of the widely used methods.
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. Wherein the barrier-type thermal barrier coating achieves 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 hollow glass microballoon is a glass ball shell with thin wall and sealing, and the interior of the shell is vacuum or is wrapped with various gases, so the hollow glass microballoon has the characteristics of light weight, heat insulation, insulation and the like, and is widely applied to heat insulation coatings. Compared with hollow ceramic microspheres, the hollow glass microspheres are easy to break and lose efficacy due to thin walls in the preparation process of the coating, so that the doping amount of the hollow glass microspheres has to be increased; however, the outer wall of the micron-sized hollow ceramic microsphere is provided with holes, so that the hollow structure of the hollow ceramic microsphere can penetrate into a part in the aqueous emulsion, and the heat insulation property of the hollow ceramic microsphere is further reduced. In addition, the hollow glass beads have a small specific gravity, and are easily floated on the surface of a water-based coating system and are difficult to disperse. Therefore, the common water-based heat insulation coating needs to add more than 40% of hollow glass beads to obtain good heat insulation effect. However, the large amount of the hollow glass beads causes the paint to fall off and lose efficacy rapidly due to poor adhesion after short-term actual service.
Disclosure of Invention
In view of the above, the present invention aims to provide a water-based heat-insulating reflective composite coating with a very small amount of powder filler, which not only has a very low thermal conductivity, but also has strong weather resistance and long actual service life.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a water-based heat-insulation reflective composite coating with low thermal conductivity coefficient comprises the following raw materials: 40-60% of organic silicon modified acrylic emulsion, 6-10% of modified ceramic coated hollow glass microspheres, 10-15% of titanium dioxide, 10-15% of talcum powder, 5-15% of deionized water and the balance of auxiliary agent in percentage by weight; the hollow glass bead coated with the modified ceramic has the structure that the surface of the hollow glass bead is sequentially coated with a ceramic layer and a fluorosilicone layer.
In the technical scheme, the organosilicon modified acrylic emulsion is formed by polymerizing an organosilicon monomer containing an unsaturated bond and acrylic, wherein the organosilicon 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 ratio of organosilicon 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, the film forming assistant can be dodecyl alcohol ester, the dispersing agent can be siloxane, the anti-flash rust inhibitor can be organic zinc chelate, the defoaming agent can be water-based organosilicon, and the leveling agent can be dimethyl siloxane.
Furthermore, in the above technical solution, the hollow glass beads are made of alkali silicate glass (pH is about 9.5), and have a thermal conductivity of 0.2 w/(m.K) or less and an average particle size of 35 μm or less. For example, K1, K20, S38HS series of 3M company can be selected.
Further, in the above technical solution, the ceramic layer is an aluminum nitride layer, and the fluorosilicone layer is a perfluorooctyltriethoxysilane layer.
Furthermore, the preparation method of the modified ceramic-coated hollow glass bead comprises the following steps:
the method comprises the following steps: the surface of the hollow glass microsphere is pretreated to enable the hollow glass microsphere to have negative charges, and the surface of the hollow glass microsphere is pretreated to enable the aluminum nitride powder to have positive charges;
step two: mixing the pretreated hollow glass beads with aluminum nitride powder, wrapping the aluminum nitride on the surfaces of the hollow glass beads through electrostatic adsorption, drying and calcining the hollow glass beads;
step three: and (3) performing surface modification on the ceramic-coated hollow glass microspheres prepared in the second step by adopting perfluorooctyl triethoxysilane.
Specifically, the surface pretreatment method of the hollow glass beads comprises the following steps: firstly adding the cleaned hollow glass microspheres into a KH 570-ethanol solution for surface modification, and then adding the modified hollow glass microspheres into an ethanol-water solution of sodium polystyrene sulfonate for ultrasonic dispersion.
Specifically, the pretreatment method of the aluminum nitride powder comprises the following steps: adding aluminum nitride powder into an ethanol-water solution of poly (diallyldimethylammonium chloride), adjusting the pH to 5-7 by using thioglycolic acid, and performing ultrasonic dispersion.
Specifically, the calcining temperature is 500-650 ℃.
According to the preparation process of the aluminum nitride ceramic coated hollow glass bead, polyelectrolyte with different charges is utilized to respectively treat the surfaces of the aluminum nitride and the hollow glass bead, the aluminum nitride is coated around the hollow glass bead through electrostatic attraction, and then the core-shell structure heat-insulating filler is formed through high-temperature calcination.
The invention further provides a method for preparing the water-based heat-insulating reflective composite coating, which comprises the following steps: adding the acrylic emulsion, titanium dioxide, talcum powder and auxiliary agent into a horizontal sand mill for grinding and dispersing, then adding the modified ceramic coated hollow glass beads in batches, slowly dispersing until no floating object exists on the surface, adding deionized water to adjust the viscosity to a proper range, and finally subpackaging and sealing.
Compared with the prior art, the invention has the beneficial effects that:
1) the ceramic layer is coated on the surface of the hollow glass bead, so that the toughness of the hollow glass bead can be effectively improved, the hollow glass bead is effectively prevented from being cracked in the preparation process of the coating, and the addition amount of the hollow glass bead in the coating system is further reduced; moreover, the ceramic layer is made of a material with a lower heat conductivity coefficient, such as aluminum nitride, so that the heat insulation performance of the filler can be further improved;
2) the hollow glass microspheres coated by the perfluorinated silane modified ceramic are further adopted, so that the agglomeration and surface floating of the hollow glass microspheres in the water-based paint system can be effectively avoided, the stability of the water-based paint system is improved, and the using amount is further reduced;
3) the modified ceramic-coated hollow glass microspheres can exert effects only by 6-10%, so that the addition of resin reaches 40-60%, and the overall weather resistance and the actual service life of the coating are increased.
4) The coating disclosed by the invention adopts the modified acrylic emulsion as a main resin, the hollow glass microspheres serving as a heat-insulating functional filler and the titanium dioxide serving as a reflective functional filler are compounded for use, the viscosity and the dispersibility of the system are adjusted by the talcum powder and other auxiliaries, and the water-based coating with high stability, strong weather resistance and large heat-insulating temperature difference is obtained on the premise of extremely small addition amount of the powder.
Drawings
FIG. 1 is an SEM image of modified ceramic-coated hollow glass microspheres prepared according to the present invention;
FIG. 2 is an SEM image of a paint film formed by the water-based paint prepared by the invention.
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 composite coating in the embodiment is as follows: 50% of organosilicon modified acrylic emulsion (German Pasteur PRIMARAS-8508), 8% of modified ceramic coated hollow glass microspheres, 12% of rutile titanium dioxide, 13% of talcum powder, 2% of film forming additive (American Issman texanol), 1% of dispersant (German bike chemical DISPERBYK-2010), 2% of flash rust inhibitor (Ribend squat AKN-0660), 1% of defoaming agent (German bike chemical BYK-024), 2% of leveling agent (German bike chemical BYK-333) and 9% of deionized water in percentage by weight.
The preparation process of the modified ceramic-coated hollow glass bead comprises the following steps:
(1) preparing hollow glass bead polyelectrolyte dispersion liquid:
in this example, 3M hollow glass beads (trade name K1, thermal conductivity 0.06 w/(m.K), average particle size 32.5 μ M, and wall thickness only 0.542 μ M) were selected.
The method comprises the steps of firstly carrying out acid washing on hollow glass microspheres for 30min by using dilute hydrochloric acid to remove various impurities on the surfaces of the hollow glass microspheres, then washing the hollow glass microspheres by using a large amount of clear water, drying the hollow glass microspheres for 2h at 120 ℃, standing and cooling the hollow glass microspheres to room temperature, then adding the hollow glass microspheres into a 5 wt% KH 570-ethanol solution according to the mass ratio of 1:1 for pretreatment, stirring and dispersing the mixture for 30min at 25 ℃, and then drying the mixture for 4h at 80 ℃, wherein the surface pretreatment step is used for reducing the agglomeration among powder in the solvent in the next step. Adding 1g of hollow glass beads subjected to surface treatment into 10mL of ethanol-water solution of anionic polyelectrolyte sodium polystyrene sulfonate, and performing ultrasonic dispersion at room temperature for 30min for later use, wherein the volume ratio of ethanol to water is 3:2, and the concentration of the sodium polystyrene sulfonate is 20 wt%.
(2) Preparing aluminum nitride dispersion polyelectrolyte dispersion liquid:
firstly, 0.32g of aluminum nitride powder is added into 10mL of ethanol-water solution of cationic polyelectrolyte poly (diallyl dimethyl ammonium chloride), and the mixture is slightly stirred and dispersed; wherein the volume ratio of the ethanol to the water is 3:2, and the concentration of the poly (diallyldimethylammonium chloride) is 20 wt%. And adding a proper amount of mercaptoacetic acid serving as a stabilizer to adjust the pH value of the solution system to 5-7, and ultrasonically dispersing for 30min at room temperature for later use.
(3) The electrostatic adsorption wrapping forms a core-shell structure:
mixing the two dispersions prepared in the steps (1) and (2) according to a ratio of 1:100 (mass ratio of the hollow glass beads to the aluminum nitride), and then carrying out ultrasonic dispersion at room temperature for 30 min. And then carrying out centrifugal separation (5000r/min) on the obtained mixed solution, taking the precipitate, repeatedly carrying out centrifugal washing for 3 times by using clear water, and drying the centrifugally separated precipitate for 2 hours at the temperature of 80 ℃. And finally, preserving the heat for 2 hours at the high temperature of 550 ℃, standing and cooling the obtained powder to the room temperature to obtain the aluminum nitride ceramic coated hollow glass microspheres.
(4) Dispersing and anti-settling modification of the ceramic-coated hollow glass beads:
putting the ceramic-coated hollow glass microspheres into a perfluorooctyl triethoxysilane anhydrous carbon tetrachloride solution (the concentration can be 10-15 wt%, in this embodiment 12 wt%), wherein the mass ratio of the ceramic-coated hollow glass microspheres to the perfluorooctyl triethoxysilane is 1:100, slowly stirring for 12h at 30-50 ℃, filtering and drying to obtain the modified ceramic-coated hollow glass microspheres.
The preparation method of the water-based heat-insulating reflective composite coating comprises the following steps: 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, adding the modified ceramic coated hollow glass microspheres in batches, slowly dispersing until no floating object exists on the surface, adding deionized water to adjust the viscosity of the coating, and finally subpackaging and sealing.
The surface topography of the hollow glass microspheres before and after the ceramic coating is observed by adopting SEM, which is specifically shown in figure 1: in fig. 1, a is uncoated hollow glass beads, b is uncoated hollow glass beads after being stirred in a coating system, c is ceramic-coated hollow glass beads after being stirred in the coating system, the outer wall of the hollow glass beads coated with the ceramic surface is obviously thickened, and the outer wall is complete and not broken after being dispersedly stirred.
The coating prepared in this embodiment is coated on a substrate, the thickness of the dried coating is about 80 μm, and the surface morphology of the coating is observed by SEM, as shown in fig. 2: the hollow glass beads coated by the modified ceramic have no obvious agglomeration in a coating film, and an obvious cavity is formed after the coating is cured, so that the air content in the coating film is increased, and the excellent heat-insulating property is ensured. Secondly, detecting the heat insulation effect according to GB/T25261-2018 reflective heat insulation coating for buildings, wherein the detection results are shown in the following table:
therefore, the ceramic-coated hollow glass microspheres are used as the heat-insulation functional filler, the mechanical strength is high, the appearance can be kept complete in the stirring, dispersing and curing processes, and the ceramic-coated hollow glass microspheres are not agglomerated in a paint film after being modified and dispersed so as to form a cavity, so that the heat conductivity coefficient of a paint layer is as low as 0.038W/m.K, the heat insulation temperature difference between the paint layer and a reference blackboard is as high as 42.2 ℃, and the heat insulation effect is remarkable.
Example 2
The composition of the water-based heat-insulating reflective composite coating in the embodiment is as follows: 58% of organosilicon modified acrylic emulsion (DICwas-1070), 6% of modified titanium-coated hollow ceramic microspheres, 10% of rutile titanium dioxide, 10% 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 8% of deionized water in percentage by weight.
The procedure was as in example 1.
The paint film was examined according to the examination method of example 1, and it had a thermal conductivity of 0.040W/m.K and a thermal insulation temperature difference with the reference blackboard of 41.8 ℃.
Comparative example 1
The difference between this example and example 1 is that hollow glass beads were coated with hollow glass beads instead of modified silicon nitride.
When the coating is detected according to the detection method of example 1, the hollow glass beads in the coating film can be found to be greatly cracked through SEM, and the thermal conductivity of the coating is close to that of acrylic emulsion, which indicates that the coating has no remarkable heat insulation effect.
Comparative example 2
Different from the example 1, in the present example, the silicon nitride coated hollow glass bead is used instead of the modified silicon nitride coated hollow glass bead, that is, the dispersion anti-settling modification is not performed according to the step (4).
After the obtained product is placed for a period of time, the silicon nitride-coated hollow glass microspheres can float on the surface again, the stability of the coating is reduced, and the heat conductivity coefficient is obviously increased.
The materials listed in the invention, the values of the upper limit and the lower limit and the interval of the materials in the invention, 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 conclusion, the hollow glass beads are coated and modified, so that the toughness of the hollow glass beads is changed, the hollow glass beads are not easy to break, and meanwhile, the integrity of a middle cavity is ensured; the water-based heat-insulating reflective composite coating is prepared by further performing dispersion modification on the powder, selecting the organic silicon modified acrylic emulsion as a main resin and matching with a corresponding auxiliary agent, and the water-based heat-insulating reflective composite coating is large in heat-insulating temperature difference and excellent in long-acting effect on the premise of extremely small addition of the powder filler.
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 water-based heat-insulating reflective composite coating with low thermal conductivity is characterized by comprising the following components in percentage by weight: 40-60% of organic silicon modified acrylic emulsion, 6-10% of modified ceramic coated hollow glass microspheres, 10-15% of titanium dioxide, 10-15% of talcum powder, 5-15% of deionized water and the balance of auxiliary agent in percentage by weight; the hollow glass bead coated with the modified ceramic has the structure that the surface of the hollow glass bead is sequentially coated with a ceramic layer and a fluorosilicone layer.
2. The water-based heat-insulating reflective composite 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 an antifoaming agent, by weight.
3. The water-based heat-insulating reflective composite coating as claimed in claim 2, wherein the film-forming assistant is a dodecanol ester, the dispersant is a siloxane, the flash rust inhibitor is an organic zinc chelate, the defoamer is an aqueous silicone, and the leveling agent is a dimethyl siloxane.
4. The water-based heat-insulating reflective composite coating as claimed in claim 1, wherein the hollow glass beads are made of alkali silicate glass, and have a thermal conductivity of 0.2 w/(m.K) or less and an average particle size of 35 μm or less.
5. The aqueous heat-insulating reflective composite coating according to claim 1, wherein the ceramic layer is an aluminum nitride layer, and the fluorosilicone layer is a perfluorooctyltriethoxysilane layer.
6. The water-based heat-insulating reflective composite coating as claimed in claim 5, wherein the preparation method of the modified ceramic-coated hollow glass microspheres comprises:
the method comprises the following steps: the surface of the hollow glass microsphere is pretreated to enable the hollow glass microsphere to have negative charges, and the surface of the hollow glass microsphere is pretreated to enable the aluminum nitride powder to have positive charges;
step two: mixing the pretreated hollow glass beads with aluminum nitride powder, wrapping the aluminum nitride on the surfaces of the hollow glass beads through electrostatic adsorption, drying and calcining the hollow glass beads;
step three: and (3) performing surface modification on the ceramic-coated hollow glass microspheres prepared in the second step by adopting perfluorooctyl triethoxysilane.
7. The water-based heat-insulating reflective composite coating as claimed in claim 6, wherein the surface pretreatment method of the hollow glass beads in step one is as follows: firstly, adding the cleaned hollow glass microspheres into KH 570-ethanol solution for surface modification, and then adding the modified hollow glass microspheres into ethanol-water solution of sodium polystyrene sulfonate for ultrasonic dispersion.
8. The aqueous heat-insulating reflective composite coating according to claim 6, wherein the pretreatment method of the aluminum nitride powder in the first step comprises: adding aluminum nitride powder into an ethanol-water solution of poly (diallyldimethylammonium chloride), adjusting the pH to 5-7 by using thioglycolic acid, and performing ultrasonic dispersion.
9. The water-based heat-insulating reflective composite coating as claimed in claim 6, wherein the calcination is 500-650 ℃.
10. The preparation method of the water-based heat-insulating reflective composite coating as claimed in any one of claims 1 to 9, wherein the acrylic emulsion, the titanium white, the talcum powder and the auxiliary agent are firstly added into a horizontal sand mill for grinding and dispersing, then the modified ceramic-coated hollow glass beads are added in batches and slowly dispersed until no floating matter exists on the surface, and then deionized water is added and uniformly stirred, and then the mixture is packaged and stored.
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| CN116854488A (en) * | 2023-07-18 | 2023-10-10 | 丹东播磨耐火材料有限公司 | Magnesia carbon brick and preparation method thereof |
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