CN114213948A - Contains hollow SiO2@TiO2Preparation method of microsphere photocuring waterborne polyurethane heat-insulating coating - Google Patents
Contains hollow SiO2@TiO2Preparation method of microsphere photocuring waterborne polyurethane heat-insulating coating Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 238000000576 coating method Methods 0.000 title claims abstract description 69
- 239000004814 polyurethane Substances 0.000 title claims abstract description 68
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 36
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 24
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 24
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 24
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 94
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
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- 239000011737 fluorine Substances 0.000 claims description 12
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 238000003848 UV Light-Curing Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001914 filtration Methods 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
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- 238000003786 synthesis reaction Methods 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
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- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- 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
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- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a hollow SiO-containing material2@TiO2A preparation method of a microsphere photocuring waterborne polyurethane heat insulation coating belongs to the technical field of preparation of heat insulation waterborne polyurethane. Firstly, preparing a polystyrene template by a dispersion polymerization method, and respectively preparing PS @ SiO by a sol-gel method2And PS @ SiO2@TiO2Microspheres, and then preparing PS @ SiO with a multilayer micro-nano structure by a solvothermal method2@TiO2Microspheres, and finally calcining to prepare hollow multilayer micro-nano structure SiO2@TiO2Microspheres HSTs; then curing the film as a part of a coating film of polyurethane to obtain the hollow SiO-containing film2@TiO2A microsphere photo-curing water-based polyurethane heat-insulating coating. The method can prepare the high-heat-insulation photocuring waterborne polyurethane coating, and the polyurethane can improve the heat insulation property and the weather resistance of the coating and has the advantages of high heat insulation property and high weather resistanceHas better light transmission, and can be widely applied to the fields of building glass, automobile glass and the like with high requirements on heat insulation and light transmission.
Description
Technical Field
The invention relates to a hollow SiO-containing material2@TiO2A preparation method of a microsphere photocuring waterborne polyurethane heat insulation coating belongs to the technical field of preparation of heat insulation waterborne polyurethane.
Background
Along with the improvement of awareness of people on environmental protection, energy conservation and emission reduction, the energy conservation and the use arouse attention of people. In the aspect of building coating, the thermal insulation coating can effectively reduce carbon emission, so that the market of the thermal insulation coating is particularly wide. In order to enhance the heat insulation effect of the material, the traditional coating usually adds a barrier filler with low thermal conductivity into a resin matrix. The hollow glass microspheres and the hollow glass ceramic microspheres break the continuity of a heat transfer path due to the existence of high-density air holes, can effectively reduce the heat conductivity coefficient of the material, and can effectively enhance the heat insulation performance of the coating due to the rapid technical development.
However, since the thicker volume of this type of coating deteriorates other properties of the coating, studies have shown that the effect of the heat conductivity of a single degraded coating on the thermal insulation coating of a building is limited, and the building still lacks a good resistance to the heat of solar radiation, and therefore, reflective fillers also play an important role in building insulation. The high-performance composite coating with multiple mechanisms synergistic action is the research direction of the heat-insulating coating.
Chemical composition of SiO2And TiO2Due to the respective characteristics, the heat-insulating material has good heat-insulating property. SiO 22As a barrier filler, has a low thermal conductivity that slows the thermal motion between solids, between gases in gaps, and between gases and solids in a film. TiO 22Is a reflective filler having the ability to effectively reflect infrared light, and most of the light entering the film is reflected and scattered to reduce its accumulated heat, which effectively suppresses heat transfer, reduces heat absorption of the film, and thus achieves thermal insulation.
Disclosure of Invention
The invention aims to overcome the defects and provide a hollow SiO-containing material2@TiO2The preparation method of the microsphere photo-curing waterborne polyurethane heat-insulating coating can improve the heat-insulating property and weather resistance of the coating and has better light transmittance.
The technical scheme of the invention is that the hollow SiO-containing film2@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized by comprising the following steps: firstly, preparing a polystyrene template by a dispersion polymerization method, and respectively preparing PS @ SiO by a sol-gel method2And PS @ SiO2@TiO2Microspheres, and then preparing PS @ SiO with a multilayer micro-nano structure by a solvothermal method2@TiO2Microspheres, and finally calcining to prepare hollow multilayer micro-nano structure SiO2@TiO2Microspheres HSTs; then curing the film as a part of a coating film of polyurethane to obtain the hollow SiO-containing film2@TiO2A microsphere photo-curing water-based polyurethane heat-insulating coating.
The method comprises the following steps:
(1) preparing polystyrene template microspheres: uniformly stirring a dispersing agent, an initiator and deionized water in a reaction container, introducing nitrogen to remove oxygen in a system, adding styrene under the protection of nitrogen, carrying out condensation reflux and gradual temperature rise reaction, and cooling to room temperature by using an ice bath after the reaction is finished; filtering to remove large-size aggregates, then performing multiple deionization washing, centrifuging, and drying in a vacuum oven to obtain polystyrene template microspheres;
(2)TiO2coated SiO2Synthesis of a coated PS template: magnetically stirring ethanol and the polystyrene template microspheres prepared in the step (1), adding ammonia monohydrate, and then adding a silicon dioxide precursor dispersed in the ethanol for stirring reaction; finally adding a titanium dioxide precursor dispersed in ethanol, and continuously stirring for reaction to obtain PS @ SiO2@TiO2Microspheres;
(3) preparing HSTs microspheres with multilayer micro-nano structures: firstly, PS @ SiO prepared in step (2)2@TiO2Adding the microspheres and hexamethylenetetramine into a reaction vessel containing isopropanol, and ultrasonically dispersing at room temperature to form a uniform mixed system(ii) a Slowly dripping a titanium dioxide precursor into the mixture under magnetic stirring, transferring the mixture into a high-pressure kettle, reacting at high temperature and high pressure, and naturally cooling to room temperature; washing the precipitate with anhydrous ethanol for three times, centrifuging and collecting; calcining the dried product, and removing the polystyrene core to obtain HSTs microspheres with multilayer micro-nano structures;
(4) preparing a photocuring waterborne polyurethane heat-insulating coating: mixing the HSTs microspheres of the multilayer micro-nano structure prepared in the step (3) and a photoinitiator with a photocuring aqueous fluorinated polyurethane emulsion, uniformly dispersing under a dark condition, coating the mixture in a glass sheet and a polytetrafluoroethylene groove, standing at room temperature, drying in an oven at 60-80 ℃ for 20-40min, and finally curing the coating in a UV curing machine for 30-60s to obtain the hollow SiO-containing polyurethane emulsion2@TiO2A microsphere photo-curing water-based polyurethane heat-insulating coating.
The dispersing agent is one of polyvinylpyrrolidone and polyvinyl alcohol;
the initiator is specifically one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline;
the photoinitiator was 1173 photoinitiator.
The silicon dioxide precursor is specifically one or more of tetraethoxysilane, tetramethoxysilane and propyl orthosilicate.
The titanium dioxide precursor is specifically one or more of tetrabutyl titanate, isopropyl titanate, titanium tetrachloride and isobutyl titanate.
The step (1) is as follows: boiling deionized water, and deoxidizing for later use; 4.1 to 4.2g of dispersant, 0.04 to 0.05g of initiator and 240 plus 260g of deionized water are sequentially added into a reaction vessel and are magnetically stirred uniformly at 200 plus 400 rpm; introducing nitrogen to remove oxygen in the system, adding 24.5-25.5g of styrene St under the protection of nitrogen, condensing and refluxing, gradually heating to 68-72 ℃, keeping the temperature for 22-26h, stopping the reaction, and cooling to room temperature by using an ice bath; filtering to remove large-size aggregates, performing deionization washing and centrifugation for several times, and drying in a vacuum oven at 40-50 deg.C under 0.08-0.1MPa for 22-26h to obtain polystyrene template microspheres.
The step (2) is as follows: magnetically stirring 180-200g of ethanol and 11.5-12.5g of polystyrene template microspheres prepared in the step (1) for 14-16 minutes, then adding 2.9-3mL of ammonia monohydrate, then adding 9-10mL of silica precursor dispersed in 9-10mL of ethanol, and violently stirring for reacting for 22-26 hours, wherein the temperature is kept at 34-36 ℃; adding 9-10mL of titanium dioxide precursor dispersed in 9-10mL of ethanol, reacting and stirring vigorously for 24h, and keeping the temperature at 34-36 ℃; finally, decompressing and distilling at 65-70 ℃ and 0.08-0.09MPa, and evaporating the solvent to obtain PS @ SiO2@TiO2And (3) microspheres.
The step (3) is as follows: 0.09-0.1g of PS @ SiO prepared in step (2)2@TiO2Adding the microspheres and 0.55-0.56g of HMTA into a reaction vessel containing 30mL of isopropanol, and ultrasonically dispersing for 12-16min at 28KHz at room temperature to form a uniform mixed system; slowly dripping 2.9-3.1mmol of titanium dioxide precursor into the mixture under magnetic stirring; then transferring the mixture into a high-pressure kettle, heating the mixture in an oven at 200 ℃ under the pressure of 0.08-0.1MPa for 22-26h, and naturally cooling the mixture in the oven to room temperature; washing the precipitate with anhydrous ethanol for three times, centrifuging and collecting; and finally, calcining the dried product in air at 500 ℃ for 2-4h, and removing the polystyrene core to obtain the HSTs microspheres with the multilayer micro-nano structure.
The step (4) is as follows: firstly, taking photocuring aqueous fluorine-containing polyurethane emulsion, mixing HSTs microspheres accounting for 0-5% of the mass of the aqueous fluorine-containing polyurethane emulsion and a photoinitiator accounting for 2-5% of the mass of the aqueous fluorine-containing polyurethane emulsion, uniformly dispersing under the dark condition, then coating the mixture on a carrier, standing at room temperature, drying in an oven at 60-80 ℃ for 20-40min, and finally, putting a coating film into a UV curing machine for curing for 30-60s to obtain the hollow SiO-containing polyurethane emulsion2@TiO2A microsphere photo-curing water-based polyurethane heat-insulating coating.
The SiO-containing hollow film prepared by the method2@TiO2The microsphere photo-curing water-based polyurethane heat-insulating coating is applied to building glass or automobile glass.
Multilayer wiener structure TiO2Coated SiO2In the aspect of structure of hollow microspheres (HSTs), firstly, multilayer TiO on the surface of HSTs is utilized2Nano meterA large number of pores are formed between the sheet and the PU matrix to store air, so that the heat conductivity coefficient of the PU film is reduced, and the effect is similar to the warm keeping effect of down in a down jacket. In addition, the irregular lamellar structure of titanium dioxide increases the probability of multiple levels of reflection and scattering of light. Second, SiO2Shell layer and TiO2The heterostructure of the shell layer also produces multi-level reflection and scattering of light. Finally, the existence of the cavity structure further reduces the heat conductivity coefficient of the film, increases multi-level reflection, and greatly improves the heat insulation performance of the film due to the synergistic effect of the layered structure.
The invention has the beneficial effects that: the method can prepare the high-heat-insulation waterborne polyurethane coating. The polyurethane can improve the heat insulation property and the weather resistance of the coating, has better light transmission property, and can be widely applied to the fields of building glass, automobile glass and the like with high requirements on heat insulation and light transmission.
Drawings
FIG. 1 TEM morphology of HSTs microspheres prepared according to example 1 of the present invention.
FIG. 2 is a schematic partial enlarged view of TEM morphology of HSTs microspheres prepared in example 1 of the present invention.
FIG. 3 is a graphical representation of wavelength-reflectivity as a function of microsphere content of HSTs in accordance with an embodiment of the present invention.
FIG. 4 is a temperature-time diagram of the thermal insulation test of polyurethane containing 5% of HSTs microspheres with no polyurethane coating according to the present invention.
Detailed Description
Example 1
(1) Preparation of Polystyrene (PS) template: firstly, boiling deionized water for deoxidization treatment for standby. 4.12g of polyvinylpyrrolidone (PVP), 0.05g of azobisisobutylamidine hydrochloride (AIBA) and 250mL of deionized water were added in sequence to a three-necked flask and stirred magnetically (300rpm) until homogeneous. And introducing nitrogen to remove oxygen in the system, adding 25g of styrene (St) under the protection of nitrogen, carrying out condensation reflux, gradually heating to 70 ℃, keeping the temperature for 24 hours, stopping the reaction, and cooling to room temperature by using an ice bath. Filtering with filter cloth to remove large-size aggregates, performing multiple deionization washing and centrifugation, and drying in a vacuum oven at 45 deg.C for 24h to obtain PS microsphere template;
(2)TiO2coated SiO2Synthesis of a coated PS template: 190g of ethanol and 12g of the prepared PS template were magnetically stirred for 15min, then 3mL of ammonia monohydrate were added, followed by 20mL of tetraethoxysilane solution (10mL of tetraethoxysilane in 10mL of ethanol), the reaction was stirred vigorously for 24h, and the temperature was kept at 35 ℃. Finally 20mL of tetrabutyltitanate solution (10mL of tetrabutyltitanate in 10mL of ethanol) are added and the reaction is stirred vigorously for 24h, the temperature being kept at 35 ℃. Finally, the solvent is distilled and evaporated under reduced pressure at 70 ℃ to obtain PS @ SiO2@TiO2A ball;
(3) preparing an HSTs microsphere material with a multilayer micro-nano structure: 0.1g of PS @ SiO2@TiO2The spheres and 4.0mmol of Hexamethylenetetramine (HMTA) were added to a 30mL isopropanol beaker and ultrasonically dispersed at room temperature for 15min to form a homogeneous mixed system. Then, a certain amount of TBOT was slowly dropped into the mixture under magnetic stirring. The mixture was then transferred to a teflon lined stainless steel autoclave with a capacity of 100 mL. The reaction was carried out by heating in an oven at 200 ℃ for 24 h. The oven was then allowed to cool naturally to room temperature. The precipitate was washed three times with absolute ethanol and collected by centrifugation. Finally, calcining the dried product in air at 500 ℃ for 3h to obtain HSTs microspheres;
TEM morphology of HSTs microspheres is shown in FIG. 1, and a partially enlarged schematic view is shown in FIG. 2. As shown in the figure 1-2, the surface of the HSTs microsphere with the multi-layer micro-nano structure is not only attached with a titanium dioxide shell layer, but also the titanium dioxide shell layer at the outermost layer presents a multi-layer flaky flower-like structure.
(4) Preparing a photocuring waterborne polyurethane heat-insulating coating: firstly, taking HSTs microspheres with different mass (0, 1%, 2%, 3%, 4%, 5%, 6%) concentrations based on the mass of PU, dispersing in 20mL of deionized water, and performing ultrasonic action for 15 min. Then, adding the HSTs suspension and 40g of the water-based photo-curing polyurethane emulsion into a 100mL three-necked flask, stirring for 5h at 60 ℃, finally adding 2% of photoinitiator 1173 by mass of PU into the mixed latex, then coating the latex in a glass sheet and a polytetrafluoroethylene groove, standing at room temperature, drying in an oven at 60 ℃ for 40min, and finally placing the coating in a UV curing machine for curing for 45s to obtain the hollow SiO-containing polyurethane emulsion2@TiO2Light of microspheresAnd curing the waterborne polyurethane heat-insulating coating.
The PU coating films of HSTs microspheres with different contents are measured by an ultraviolet-visible light-infrared spectrophotometer to obtain an infrared reflection spectrum, and the specific test result is shown in figure 3. As can be seen from fig. 3, the polyurethane coating with the addition of the HSTs has a higher reflectivity in the infrared band compared to the polyurethane coating without the HSTs, indicating that the coating has a good thermal effect in blocking infrared, and generally increases with the HSTs content. When the content of the HSTs is 5%, the reflectivity is highest, probably because the HSTs with the concentration of 5% is dispersed in the PU resin system most uniformly, and the particles with the concentration of more than 5% lose the advantages brought by the nanometer size because the agglomeration phenomenon reduces the specific surface area contacted with the infrared ray, thereby reducing the reflectivity of the infrared band.
And (3) carrying out an outdoor heat insulation performance simulation test on the polyurethane coating film and the PU coating film with the content of 5% of HSTs. The actual heat insulation effect of the coating is explored by adopting a heat insulation device. Firstly, placing an experimental glass plate in a heat preservation groove, starting a 300W infrared lamp at the top to simulate a sunlight source, and measuring the real-time temperature in the heat insulation device every 1 min.
The specific test result is shown in fig. 4, the temperature of the polyurethane composite coating with the content of 5% of HSTs is stably lowered by more than 15 ℃ after 10min compared with that of the common polyurethane coating, and the excellent outdoor heat insulation capability is shown.
Example 2
(1) Preparing polystyrene template microspheres: boiling deionized water, and deoxidizing for later use; 4.1g of dispersing agent, 0.04g of initiator and 240g of deionized water are sequentially added into a reaction vessel, and the mixture is magnetically stirred uniformly at 200 rpm; introducing nitrogen to remove oxygen in the system, adding 24.5g of styrene St under the protection of nitrogen, condensing and refluxing, gradually heating to 68 ℃, keeping the temperature for 22 hours, stopping the reaction, and cooling to room temperature by using an ice bath; filtering to remove large-size aggregates, then carrying out deionization washing and centrifugation for several times, and drying in a vacuum oven at 40 ℃ for 22h under 0.08MPa to obtain the polystyrene template microspheres.
(2)TiO2Coated SiO2Synthesis of a coated PS template: 180g of ethanol and 11.5g of stepMagnetically stirring the polystyrene template microspheres prepared in the step (1) for 14min, then adding 2.9mL of ammonia monohydrate, then adding 9mL of silicon dioxide precursor dispersed in 9mL of ethanol, and reacting for 22h under vigorous stirring, wherein the temperature is kept at 34 ℃; adding 9mL of titanium dioxide precursor dispersed in 9mL of ethanol, reacting vigorously and stirring for 24h, and keeping the temperature at 34 ℃; finally, decompressing and distilling at 65 ℃ and 0.08MPa, and evaporating the solvent to obtain PS @ SiO2@TiO2And (3) microspheres.
(3) Preparing HSTs microspheres with multilayer micro-nano structures: 0.09g of PS @ SiO prepared in step (2)2@TiO2Adding the microspheres and 0.55g of HMTA into a reaction vessel containing 30mL of isopropanol, and ultrasonically dispersing for 12min at 28KHz at room temperature to form a uniform mixed system; slowly dripping 2.9mmol of titanium dioxide precursor into the mixture under magnetic stirring; then transferring the mixture into a high-pressure kettle, heating the mixture in an oven at 200 ℃ under 0.08MPa for 22h, and naturally cooling the mixture in the oven to room temperature; washing the precipitate with anhydrous ethanol for three times, centrifuging and collecting; and finally, calcining the dried product in air at 500 ℃ for 2h, and removing the polystyrene core to obtain the HSTs microspheres with the multilayer micro-nano structure.
(4) Preparing a photocuring waterborne polyurethane heat-insulating coating: firstly, taking water-based fluorine-containing polyurethane emulsion, mixing HSTs microspheres accounting for 5% of the water-based fluorine-containing polyurethane emulsion and a photoinitiator accounting for 2% of the water-based fluorine-containing polyurethane emulsion, uniformly dispersing under the condition of keeping out of the sun, then coating the mixture in a carrier, standing at room temperature, drying in an oven at 60 ℃ for 20min, and finally, putting the coating film in a UV curing machine for curing for 30s to obtain the hollow SiO-containing polyurethane emulsion2@TiO2A microsphere photo-curing water-based polyurethane heat-insulating coating.
The dispersing agent is polyvinylpyrrolidone;
the initiator is specifically azodiisobutyl imidazoline hydrochloride;
the photoinitiator is 1173 photoinitiator;
the silicon dioxide precursor is specifically tetramethoxysilane;
the titanium dioxide precursor is specifically titanium tetrachloride.
Example 3
(1) Preparing polystyrene template microspheres: boiling deionized water, and deoxidizing for later use; 4.2g of dispersant, 0.05g of initiator and 260g of deionized water are sequentially added into a reaction vessel, and the mixture is magnetically stirred uniformly at 400 rpm; introducing nitrogen to remove oxygen in the system, adding 25.5g of styrene St under the protection of nitrogen, condensing and refluxing, gradually heating to 72 ℃, keeping the temperature for 26 hours, stopping the reaction, and cooling to room temperature by using an ice bath; filtering to remove large-size aggregates, then carrying out deionization washing and centrifugation for several times, and drying in a vacuum oven at 50 ℃ for 26h under 0.1MPa to obtain the polystyrene template microspheres.
(2)TiO2Coated SiO2Synthesis of a coated PS template: magnetically stirring 200g of ethanol and 12.5g of polystyrene template microspheres prepared in the step (1) for min, then adding 3mL of ammonia monohydrate, then adding 10mL of silicon dioxide precursor dispersed in 10mL of ethanol, and carrying out vigorous stirring reaction for 26h, wherein the temperature is kept at 36 ℃; adding 10mL of titanium dioxide precursor dispersed in 10mL of ethanol, reacting vigorously and stirring for 24h, and keeping the temperature at 36 ℃; finally, the PS @ SiO is obtained by adopting reduced pressure distillation at 70 ℃ and 0.09MPa and evaporating the solvent2@TiO2And (3) microspheres.
(3) Preparing HSTs microspheres with multilayer micro-nano structures: 0.1g of PS @ SiO prepared in step (2)2@TiO2Adding the microspheres and 0.56g of HMTA into a reaction vessel containing 30mL of isopropanol, and ultrasonically dispersing for 16min at 28KHz at room temperature to form a uniform mixed system; slowly dripping 3.1mmol of titanium dioxide precursor into the mixture under magnetic stirring; then transferring the mixture into an autoclave, heating the mixture in an oven at 200 ℃ under 0.1MPa for 26h, and naturally cooling the mixture in the oven to room temperature; washing the precipitate with anhydrous ethanol for three times, centrifuging and collecting; and finally, calcining the dried product in air at 500 ℃ for 4h, and removing the polystyrene core to obtain the HSTs microspheres with the multilayer micro-nano structure.
(4) Preparing a photocuring waterborne polyurethane heat-insulating coating: firstly, taking photo-curing aqueous fluorine-containing polyurethane emulsion, mixing HSTs microspheres accounting for 5 percent of the mass of the photo-curing aqueous fluorine-containing polyurethane emulsion and a photoinitiator accounting for 5 percent of the mass of the mixed photo-curing aqueous fluorine-containing polyurethane emulsion, and keeping out of the sun under the condition of lightDispersing uniformly, coating the mixture in a carrier, standing at room temperature, drying in an oven at 80 ℃ for 40min, and curing the coating in a UV curing machine for 60s to obtain the hollow SiO-containing material2@TiO2A microsphere photo-curing water-based polyurethane heat-insulating coating.
The dispersing agent is polyvinyl alcohol;
the initiator is azodicyano valeric acid;
the photoinitiator was 1173 photoinitiator.
The silicon dioxide precursor is propyl orthosilicate.
The titanium dioxide precursor is specifically isobutyl titanate.
Claims (10)
1. Contains hollow SiO2@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized by comprising the following steps: firstly, preparing a polystyrene template by a dispersion polymerization method, and respectively preparing PS @ SiO by a sol-gel method2And PS @ SiO2@TiO2Microspheres, and then preparing PS @ SiO with a multilayer micro-nano structure by a solvothermal method2@TiO2Microspheres, and finally calcining to prepare hollow multilayer micro-nano structure SiO2@TiO2Microspheres HSTs; then curing the film as a part of a coating film of polyurethane to obtain the hollow SiO-containing film2@TiO2A microsphere aqueous polyurethane heat-insulating coating.
2. The hollow SiO-containing SiO-coated steel sheet as claimed in claim 12@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized by comprising the following steps:
(1) preparing polystyrene template microspheres: uniformly stirring a dispersing agent, an initiator and deionized water in a reaction container, introducing nitrogen to remove oxygen in a system, adding styrene under the protection of nitrogen, carrying out condensation reflux and gradual temperature rise reaction, and cooling to room temperature by using an ice bath after the reaction is finished; filtering to remove large-size aggregates, then performing multiple deionization washing, centrifuging, and drying in a vacuum oven to obtain polystyrene template microspheres;
(2)TiO2coated SiO2Synthesis of a coated PS template: magnetically stirring ethanol and the polystyrene template microspheres prepared in the step (1), adding ammonia monohydrate, and then adding a silicon dioxide precursor dispersed in the ethanol for stirring reaction; finally adding a titanium dioxide precursor dispersed in ethanol, and continuously stirring for reaction to obtain PS @ SiO2@TiO2Microspheres;
(3) preparing HSTs microspheres with multilayer micro-nano structures: firstly, PS @ SiO prepared in step (2)2@TiO2Adding the microspheres and hexamethylenetetramine into a reaction vessel containing isopropanol, and ultrasonically dispersing at room temperature to form a uniform mixed system; slowly dripping a titanium dioxide precursor into the mixture under magnetic stirring, transferring the mixture into a high-pressure kettle, reacting at high temperature and high pressure, and naturally cooling to room temperature; washing the precipitate with anhydrous ethanol for three times, centrifuging and collecting; calcining the dried product, and removing the polystyrene core to obtain HSTs microspheres with multilayer micro-nano structures;
(4) preparing a photocuring waterborne polyurethane heat-insulating coating: mixing the HSTs microspheres of the multilayer micro-nano structure prepared in the step (3) and a photoinitiator with a water-based fluorinated polyurethane emulsion, uniformly dispersing under a dark condition, coating the mixture in a glass sheet and a polytetrafluoroethylene groove, standing at room temperature, drying in an oven at 60-80 ℃ for 20-40min, and finally curing the coating in a UV curing machine for 30-60s to obtain the hollow SiO-containing polyurethane emulsion2@TiO2A microsphere photo-curing water-based polyurethane heat-insulating coating.
3. The method of claim 2, wherein the SiO in the hollow core is contained2@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized by comprising the following steps: the dispersing agent is one of polyvinylpyrrolidone and polyvinyl alcohol;
the initiator is specifically one of azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid and azobisisopropylimidazoline;
the photoinitiator was 1173 photoinitiator.
4. As in claimThe hollow SiO-containing film of claim 22@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized by comprising the following steps: the silicon dioxide precursor is specifically one or more of tetraethoxysilane, tetramethoxysilane and propyl orthosilicate.
5. The method of claim 2, wherein the SiO in the hollow core is contained2@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized by comprising the following steps: the titanium dioxide precursor is specifically one or more of tetrabutyl titanate, isopropyl titanate, titanium tetrachloride and isobutyl titanate.
6. The method of claim 2, wherein the SiO in the hollow core is contained2@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized in that the step (1) is as follows: boiling deionized water, and deoxidizing for later use; 4.1 to 4.2g of dispersant, 0.04 to 0.05g of initiator and 240 plus 260g of deionized water are sequentially added into a reaction vessel and are magnetically stirred uniformly at 200 plus 400 rpm; introducing nitrogen to remove oxygen in the system, adding 24.5-25.5g of styrene St under the protection of nitrogen, condensing and refluxing, gradually heating to 68-72 ℃, keeping the temperature for 22-26h, stopping the reaction, and cooling to room temperature by using an ice bath; filtering to remove large-size aggregates, performing deionization washing and centrifugation for several times, and drying in a vacuum oven at 40-50 deg.C under 0.08-0.1MPa for 22-26h to obtain polystyrene template microspheres.
7. The method of claim 2, wherein the SiO in the hollow core is contained2@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized in that the step (2) is as follows: magnetically stirring 180-200g of ethanol and 11.5-12.5g of polystyrene template microspheres prepared in the step (1) for 14-16min, then adding 2.9-3mL of ammonia monohydrate, then adding 9-10mL of silica precursor dispersed in 9-10mL of ethanol, and violently stirring for reacting for 22-26h, wherein the temperature is kept at 34-36 ℃; adding 9-10mL of titanium dioxide precursor dispersed in 9-10mL of ethanol, reacting and stirring vigorously for 24h, and keeping the temperature at 34-36 ℃; finally, vacuum distilling at 65-70 deg.C and 0.08-0.09MPa, and evaporating solventObtaining PS @ SiO2@TiO2And (3) microspheres.
8. The method of claim 2, wherein the SiO in the hollow core is contained2@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized in that the step (3) is as follows: 0.09-0.1g of PS @ SiO prepared in step (2)2@TiO2Adding the microspheres and 0.55-0.56g of HMTA into a reaction vessel containing 30mL of isopropanol, and ultrasonically dispersing for 12-16min at 28KHz at room temperature to form a uniform mixed system; slowly dripping 2.9-3.1mmol of titanium dioxide precursor into the mixture under magnetic stirring; then transferring the mixture into a high-pressure kettle, heating the mixture in an oven at 200 ℃ under the pressure of 0.08-0.1MPa for 22-26h, and naturally cooling the mixture in the oven to room temperature; washing the precipitate with anhydrous ethanol for three times, centrifuging and collecting; and finally, calcining the dried product in air at 500 ℃ for 2-4h, and removing the polystyrene core to obtain the HSTs microspheres with the multilayer micro-nano structure.
9. The method of claim 2, wherein the SiO in the hollow core is contained2@TiO2The preparation method of the microsphere photocuring waterborne polyurethane heat-insulating coating is characterized by comprising the following steps (4): firstly, mixing water-based fluorine-containing polyurethane emulsion, HSTs microspheres accounting for 0-5% of the mass of the water-based fluorine-containing polyurethane emulsion and a photoinitiator accounting for 2-5% of the mass of the water-based fluorine-containing polyurethane emulsion, uniformly dispersing under the condition of keeping out of the sun, then coating the mixture on a carrier, standing at room temperature, drying in an oven at 60-80 ℃ for 20-40min, and finally, putting a coating film into a UV curing machine for curing for 30-60s to obtain the hollow SiO-containing coating2@TiO2A microsphere photo-curing water-based polyurethane heat-insulating coating.
10. Hollow-containing SiO obtainable by a process according to one of claims 1 to 92@TiO2The microsphere aqueous polyurethane heat-insulating coating is characterized by comprising the following components in parts by weight: the glass is applied to building glass or automobile glass.
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