CN117986951B - Ultraviolet-resistant acrylic resin heat-insulating coating for building outer wall and preparation method thereof - Google Patents
Ultraviolet-resistant acrylic resin heat-insulating coating for building outer wall and preparation method thereof Download PDFInfo
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- CN117986951B CN117986951B CN202410170510.7A CN202410170510A CN117986951B CN 117986951 B CN117986951 B CN 117986951B CN 202410170510 A CN202410170510 A CN 202410170510A CN 117986951 B CN117986951 B CN 117986951B
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- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 56
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 40
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 242
- 239000004005 microsphere Substances 0.000 claims abstract description 146
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 121
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 58
- 239000000945 filler Substances 0.000 claims abstract description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 239000000839 emulsion Substances 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000003755 preservative agent Substances 0.000 claims abstract description 16
- 230000002335 preservative effect Effects 0.000 claims abstract description 16
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims abstract description 10
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims abstract description 10
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims abstract description 10
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 9
- 238000010521 absorption reaction Methods 0.000 claims description 58
- -1 aromatic ether compound Chemical class 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 14
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 claims description 14
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000003608 titanium Chemical class 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 229930091371 Fructose Natural products 0.000 claims description 9
- 239000005715 Fructose Substances 0.000 claims description 9
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 7
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 5
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 3
- 230000006750 UV protection Effects 0.000 abstract description 42
- 238000009413 insulation Methods 0.000 abstract description 33
- 239000004566 building material Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 29
- 230000000694 effects Effects 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 239000003973 paint Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 5
- 230000004224 protection Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LWEGEAWFSZTHML-UHFFFAOYSA-L disodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;copper Chemical compound [Na+].[Na+].[Cu].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O LWEGEAWFSZTHML-UHFFFAOYSA-L 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229940049964 oleate Drugs 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010921 in-depth analysis Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 125000000373 fatty alcohol group Chemical group 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000000215 hyperchromic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C09D5/32—Radiation-absorbing paints
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention relates to the field of building materials, and provides an ultraviolet-resistant acrylic resin heat-insulating coating for building external walls and a preparation method thereof, wherein the coating comprises, by weight, 30-60 parts of titanium dioxide microsphere coated ultraviolet-absorbing auxiliary agent composite filler, 80-110 parts of acrylic emulsion, 40-90 parts of absolute ethyl alcohol, 5-12 parts of talcum powder, 1-6 parts of toner, 2-5 parts of film forming agent, 1-3 parts of dispersing agent, 1-3 parts of defoaming agent, 0.5-2 parts of leveling agent, 0.5-2 parts of preservative and 1-3 parts of hydroxypropyl methyl cellulose, wherein the titanium dioxide microsphere coated ultraviolet-absorbing auxiliary agent filler, the absolute ethyl alcohol, the hydroxypropyl methyl cellulose, the talcum powder and the dispersing agent are uniformly stirred and mixed for standby, and then the acrylic emulsion, the toner, the film forming agent, the defoaming agent, the leveling agent and the preservative are fully and uniformly stirred. The coating disclosed by the invention has excellent heat insulation and ultraviolet resistance, and has a wide application value.
Description
Technical Field
The invention relates to the field of building materials, in particular to an ultraviolet-resistant acrylic resin heat-insulating coating for building outer walls and a preparation method thereof.
Background
Along with the enhancement of climate change and environmental awareness, the requirements of the building industry on exterior wall paint are also higher and higher, and particularly in hot summer and cold winter, the building exterior wall needs to have good heat insulation performance so as to reduce the fluctuation of indoor temperature and improve the energy efficiency. In addition, damage to building exterior wall materials from ultraviolet radiation is also an important consideration, and long-term exposure to ultraviolet radiation can lead to fading of the coating color and aging of the surface, reducing the aesthetics and durability of the building exterior wall. Therefore, searching for a building exterior wall coating capable of meeting both heat insulation and ultraviolet protection requirements is a hot spot of current research.
Acrylic resin is a polymer material having excellent physical and chemical properties, and thus has been widely used in many fields. First, the acrylic resin has good weatherability and durability, and can withstand external environmental influences under various climatic conditions. Secondly, the acrylic resin has good adhesive force and wear resistance, and can effectively protect the substrate from the external damage. In addition, the acrylic resin has good flexibility, so that the acrylic resin becomes an ideal coating material. Based on these characteristics, acrylic resins are widely used in the field of architectural coatings.
At present, the application of the acrylic resin in the building exterior wall coating has been advanced to a certain extent, and the heat insulation performance and the ultraviolet resistance of the coating can be obviously improved by adding functional additives such as heat insulation filler, ultraviolet absorber and the like into the acrylic resin. However, the current acrylic resin coating still has some defects in terms of heat insulation and ultraviolet resistance. 1. The heat insulation performance is to be improved, for example, chinese patent publication No. CN111499816A discloses a nano SiO 2 modified acrylic resin, and research results show that the modified acrylic resin has good ultraviolet shielding effect, but nano SiO 2 is solid filler and still has certain heat conductivity, so that the heat insulation performance of the modified acrylic ester is to be improved. 2. The thermal stability of the ultraviolet absorption auxiliary agent needs to be improved, and the ultraviolet absorption auxiliary agent is generally directly added in the preparation process of the traditional coating, for example, chinese patent publication No. CN108047853A discloses a coating containing the ultraviolet absorption auxiliary agent, but in practical application, the ultraviolet radiation in a high-temperature environment can cause degradation, volatilization or failure of the auxiliary agent, so that the protection effect of the material on ultraviolet is weakened. This not only affects the performance stability of the material, but can also lead to discoloration, aging, cracking, and other damage to the material. Thus, current acrylic coatings still face many challenges in terms of thermal insulation and uv resistance. In order to fill the technical blank, it is necessary to develop a novel acrylic resin coating with heat insulation and excellent ultraviolet resistance so as to meet the requirements of the building exterior wall on the high-performance acrylic resin coating.
The invention provides an ultraviolet-resistant acrylic resin heat-insulating coating for a building outer wall and a preparation method thereof, and aims to solve the problem that the current acrylic resin heat-insulating performance and ultraviolet-resistant performance are insufficient.
Disclosure of Invention
(1) Technical problem to be solved
The invention aims to provide an ultraviolet-resistant acrylic resin heat-insulating coating for an outer wall of a building and a preparation method thereof, and solves the problem that the existing acrylic resin is insufficient in heat-insulating performance and ultraviolet-resistant performance.
(2) Technical proposal
In order to achieve the above object, the present invention provides the following technical solutions:
The ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall comprises the following components in parts by weight: 30-60 parts of titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler, 80-110 parts of acrylic emulsion, 40-90 parts of absolute ethyl alcohol, 5-12 parts of talcum powder, 1-6 parts of toner, 2-5 parts of film forming agent, 1-3 parts of dispersing agent, 1-3 parts of defoaming agent, 0.5-2 parts of leveling agent, 0.5-2 parts of preservative and 1-3 parts of hydroxypropyl methyl cellulose. The average size of the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler is 50-200 nm.
Further, the preparation method of the titanium dioxide microsphere comprises the following steps: placing 10-20 parts of fructose and 2-6 parts of sodium dodecyl sulfate into 20-40 parts of mixed solution of water and absolute ethyl alcohol in a volume ratio of 1:1, uniformly stirring, placing into a high-pressure reaction kettle, performing hydrothermal reaction at 160-250 ℃ for 12-24 hours, cooling, washing, filtering and vacuum drying to obtain carbon hollow microspheres; then dissolving 20-40 parts of carbon hollow microspheres, 5-10 titanium salts and 2-6 parts of hexadecyl polyoxyethylene ether in 100 parts of absolute ethyl alcohol, uniformly stirring, then placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal reaction for 6-12h at 120-160 ℃, and then naturally cooling, carrying out suction filtration, washing and drying to obtain titanium compound-containing coated carbon hollow microspheres; finally calcining for 2-4 hours at 500-600 ℃ in air atmosphere to finally obtain the titanium dioxide microsphere with the hollow structure.
Further, the titanium salt is one or a mixture of more of sodium titanate and potassium titanate.
Further, the ultraviolet absorption auxiliary agent is 2-chloro-4-nitrophenyloxyethyl methyl cyclohexane.
Further, the preparation method of the titanium dioxide microsphere coated ultraviolet absorption auxiliary filler comprises the following steps: firstly, uniformly mixing 10-20 parts of nitrophenol and 30-60 parts of 2-bromoethanol in 50-100 parts of methylene dichloride solvent, and reacting for 2-4 hours at 50-80 ℃ to generate an aromatic ether compound; then adding 10-40 parts of 2-chloroethanol, fully and uniformly stirring, then adding 30-60 parts of titanium dioxide microspheres, reacting for 4-12 hours at 80-120 ℃, and generating 2-chloro-4-nitrophenoxy ethyl methyl cyclohexane in the hollow titanium dioxide microspheres; finally washing and vacuum drying to obtain the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler.
Further, the mass ratio of the nitrophenol to the 2-bromoethanol to the 2-chloroethanol is 1:3 (1-2).
Further, the preparation method of the acrylic emulsion comprises the following steps: according to the weight portions, 4 to 10 portions of acrylic acid, 5 to 10 portions of ethyl acrylate, 30 to 50 portions of absolute ethyl alcohol and 3 to 6 portions of sodium dodecyl benzene sulfonate are uniformly stirred to form a mixed solution, and then 2 to 4 portions of ammonium persulfate is added to form acrylic emulsion.
Further, the film forming agent is one or a mixture of more of dodecanol ester and polyethyl acrylate.
Further, the dispersing agent is one or a mixture of more of cetyl trimethyl ammonium bromide and polyethylene glycol.
Further, the defoamer is one or a mixture of more of polydimethylsiloxane, oleate and fatty alcohol polyoxyethylene ether.
Further, the leveling agent is one or a mixture of more of polydimethylsiloxane and tris (hydroxymethyl) aminomethane.
Further, the preservative is any one of benzoic acid and sodium copper ethylenediamine tetraacetate.
The invention also provides a preparation method of the ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall, which comprises the following steps:
S1, preparing acrylic emulsion: uniformly stirring acrylic acid, ethyl acrylate, absolute ethyl alcohol and sodium dodecyl benzene sulfonate to form a mixed solution, and then adding ammonium persulfate to form an acrylic emulsion for later use.
S2, preparing titanium dioxide microsphere coated ultraviolet absorption auxiliary filler: fructose and sodium dodecyl sulfate are dissolved in a mixed solution of water and absolute ethyl alcohol, and then the mixture is subjected to hydrothermal reaction at high temperature to prepare the carbon hollow microspheres. And then, mixing the carbon hollow microspheres with titanium salt and hexadecyl polyoxyethylene ether in absolute ethyl alcohol, and performing hydrothermal reaction and calcination to obtain the titanium dioxide microspheres. Finally, the nitrophenol reacts with 2-bromoethanol to generate aromatic ether compound, and then reacts with 2-chloroethanol and titanium dioxide microspheres to generate titanium dioxide microspheres coated with ultraviolet absorption auxiliary filler.
S3, dispersing solid filler: according to the proportion, the titanium dioxide microspheres are coated with ultraviolet absorption auxiliary filler, absolute ethyl alcohol, hydroxypropyl methyl cellulose, talcum powder and dispersing agent, and uniformly stirred by a stirrer to obtain uniformly dispersed solid filler for standby.
S4, preparing a coating: adding the acrylic emulsion, uniformly dispersed solid filler, titanium dioxide microsphere coated ultraviolet absorption auxiliary filler, a color enhancer, a film forming agent, a defoaming agent, a leveling agent and a preservative into a high-speed stirrer, and fully and uniformly stirring.
In the process of preparing the titanium dioxide microsphere, the composite structure containing the carbon hollow microsphere and the titanium compound is constructed by introducing the fructose, the sodium dodecyl sulfate, the titanium salt and other multicomponent materials. Secondly, the hydrothermal reaction is carried out at a higher temperature and pressure, so that uniform mixing of materials and full reaction are promoted, the crystallinity and grain size of the materials are improved, and the reaction efficiency is improved. In addition, a uniform structural layer is formed by coating titanium-containing compounds on the surfaces of the carbon hollow microspheres. The final calcination step further improves the crystal structure and stability of the material, and realizes the preparation of the titanium dioxide microsphere with a hollow structure. The preparation method realizes the preparation of the titanium dioxide microsphere with the hollow structure and has good structural stability through the construction of the multi-component material, the utilization of the hydrothermal reaction, the introduction of the coating layer and the calcination treatment.
(3) Advantageous technical effects
The ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall has the advantages that:
1. the titanium dioxide microsphere has excellent heat insulation performance, the microsphere structure has larger surface area, a heat conduction barrier layer can be formed, the heat transmission is effectively reduced, and the titanium dioxide microsphere has better heat insulation effect compared with a solid titanium dioxide microsphere.
2. When ultraviolet light irradiates the surface of the material, the titanium dioxide microspheres can absorb the ultraviolet energy and convert the ultraviolet energy into heat. The heat absorption and conduction process can further increase the heat insulation effect of the material, reduce the transmission of heat to the inside, and help to improve the thermal stability of the internal ultraviolet absorption auxiliary agent at high temperature and improve the stability and long-acting property of the ultraviolet absorption auxiliary agent.
3. The ultraviolet absorption auxiliary agents coated inside the titanium dioxide microspheres have excellent ultraviolet absorption capability, and the ultraviolet absorption auxiliary agents can further absorb ultraviolet rays, reduce the damage of the ultraviolet rays to materials and convert the energy into heat or other forms of energy.
4. Compared with the traditional solid titanium dioxide microsphere, the titanium dioxide microsphere is internally coated with the ultraviolet absorption auxiliary agent and has better heat insulation effect.
5. The titanium dioxide microsphere can also be used as an ultraviolet absorption auxiliary agent protection shell for protecting and stabilizing the ultraviolet absorption auxiliary agent, preventing the dissolution or decomposition of the absorbent and further enhancing the stability of the material. The two materials cooperate with each other, so that the heat insulation effect of the material is enhanced, and the ultraviolet protection capability of the material is improved. The synergistic effect can greatly improve the performance and stability of the material, and is widely applied to the field of building materials which are required to have heat insulation and ultraviolet resistance.
In summary, the titanium dioxide microsphere coated ultraviolet absorption auxiliary filler solves the problem that the heat insulation effect and ultraviolet resistance cannot be further improved by independently adding the heat insulation filler and the ultraviolet absorption auxiliary in the traditional coating, can realize the synergistic improvement effect of the heat insulation and the ultraviolet resistance of the acrylic resin, improves the performance and the stability of the coating for the building outer wall, and has wide application prospect in the fields of building materials and the like which need to have the heat insulation and the ultraviolet resistance functions at the same time.
Drawings
FIG. 1 is a low-profile view of hollow titanium dioxide microspheres prepared in example 1 of the present invention.
FIG. 2 is a high-power morphology graph of ultraviolet absorbing auxiliary agent wrapped by hollow titanium dioxide microspheres prepared in example 1 of the invention.
FIG. 3 is an XRD phase analysis chart of hollow titanium dioxide microspheres prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The operations in the examples were performed under conventional conditions or conditions suggested by the manufacturer without specifying specific conditions. The reagents or instruments used, if the manufacturer is not noted, are commercially available products. The parts of the invention not mentioned in the technical content will be treated with reference to the prior art. The following examples and comparative examples will be run in parallel and with the same processing steps and parameters unless otherwise indicated.
Table 1 below shows the reagents required for the examples and the corresponding purchasing companies.
Table 1 reagents required for the examples and corresponding purchasing companies
Example 1
The ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall comprises the following components in parts by weight: 30 parts of titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler, 80 parts of acrylic emulsion, 40 parts of absolute ethyl alcohol, 5 parts of talcum powder, 1 part of toner, 2 parts of film forming agent, 1 part of dispersing agent, 1 part of defoaming agent, 0.5 part of leveling agent, 0.5 part of preservative and1 part of hydroxypropyl methyl cellulose. The average size of the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler is 55nm.
The preparation method of the titanium dioxide microsphere comprises the following steps: placing 10 parts of fructose and 2 parts of sodium dodecyl sulfate into 20 parts of mixed solution of water and absolute ethyl alcohol in a volume ratio of 1:1, uniformly stirring, placing into a high-pressure reaction kettle, performing hydrothermal reaction at 160 ℃ for 12 hours, cooling, washing, filtering and vacuum drying to obtain carbon hollow microspheres; then dissolving 20 parts of carbon hollow microspheres, 5 parts of salt and 2 parts of hexadecyl polyoxyethylene ether in 100 parts of absolute ethyl alcohol, uniformly stirring, then placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal reaction for 6 hours at 120 ℃, and then naturally cooling, carrying out suction filtration, washing and drying to obtain titanium compound-containing coated carbon hollow microspheres; finally calcining for 2 hours at 500 ℃ in an air atmosphere to finally obtain the titanium dioxide microsphere with the hollow structure.
The titanium salt is sodium titanate.
The ultraviolet absorption auxiliary agent is 2-chloro-4-nitrophenyloxyethyl methyl cyclohexane.
The preparation method of the titanium dioxide microsphere coated ultraviolet absorption auxiliary filler comprises the following steps: firstly, uniformly mixing 10 parts of nitrophenol and 30 parts of 2-bromoethanol in 50 parts of dichloromethane solvent, and reacting for 2 hours at 50 ℃ to generate an aromatic ether compound; then adding 20 parts of 2-chloroethanol, fully and uniformly stirring, then adding 30 parts of titanium dioxide microspheres, reacting for 4 hours at 80 ℃, and generating 2-chloro-4-nitrophenoxy ethyl methyl cyclohexane in the hollow titanium dioxide microspheres; finally washing and vacuum drying to obtain the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler.
The mass ratio of the nitrophenol to the 2-bromoethanol to the 2-chloroethanol is 1:3:2.
The preparation method of the acrylic emulsion comprises the following steps: according to parts by weight, 4 parts of acrylic acid, 5 parts of ethyl acrylate, 30 parts of absolute ethyl alcohol and 3 parts of sodium dodecyl benzene sulfonate are uniformly stirred to form a mixed solution, and then 2 parts of ammonium persulfate is added to form an acrylic emulsion.
The film forming agent is dodecanol ester.
The dispersing agent is cetyl trimethyl ammonium bromide.
The antifoaming agent is polydimethylsiloxane.
The leveling agent is polydimethylsiloxane.
The preservative is benzoic acid.
The invention also provides a preparation method of the ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall, which comprises the following steps:
S1, preparing acrylic emulsion: uniformly stirring acrylic acid, ethyl acrylate, absolute ethyl alcohol and sodium dodecyl benzene sulfonate to form a mixed solution, and then adding ammonium persulfate to form an acrylic emulsion for later use.
S2, preparing titanium dioxide microsphere coated ultraviolet absorption auxiliary filler: fructose and sodium dodecyl sulfate are dissolved in a mixed solution of water and absolute ethyl alcohol, and then the mixture is subjected to hydrothermal reaction at high temperature to prepare the carbon hollow microspheres. And then, mixing the carbon hollow microspheres with titanium salt and hexadecyl polyoxyethylene ether in absolute ethyl alcohol, and performing hydrothermal reaction and calcination to obtain the titanium dioxide microspheres. Finally, the nitrophenol reacts with 2-bromoethanol to generate aromatic ether compound, and then reacts with 2-chloroethanol and titanium dioxide microspheres to generate titanium dioxide microspheres coated with ultraviolet absorption auxiliary filler.
S3, dispersing solid filler: according to the proportion, the titanium dioxide microspheres are coated with ultraviolet absorption auxiliary filler, absolute ethyl alcohol, hydroxypropyl methyl cellulose, talcum powder and dispersing agent, and uniformly stirred by a stirrer to obtain uniformly dispersed solid filler for standby.
S4, preparing a coating: adding the acrylic emulsion, uniformly dispersed solid filler, titanium dioxide microsphere coated ultraviolet absorption auxiliary filler, a hyperchromic agent, a film forming agent, a defoaming agent, a leveling agent and a preservative into a high-speed stirrer, and fully and uniformly stirring.
Example 2
The ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall comprises the following components in parts by weight: 40 parts of titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler, 90 parts of acrylic emulsion, 50 parts of absolute ethyl alcohol, 6 parts of talcum powder, 2 parts of toner, 3 parts of film forming agent, 1.5 parts of dispersing agent, 1.5 parts of defoaming agent, 1 part of leveling agent, 1 part of preservative and 1.5 parts of hydroxypropyl methyl cellulose. The average size of the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler is 80nm.
The preparation method of the titanium dioxide microsphere comprises the following steps: placing 10-20 parts of fructose and 2-6 parts of sodium dodecyl sulfate into 20-40 parts of mixed solution of water and absolute ethyl alcohol in a volume ratio of 1:1, uniformly stirring, placing into a high-pressure reaction kettle, performing hydrothermal reaction at 160-250 ℃ for 12-24 hours, cooling, washing, filtering and vacuum drying to obtain carbon hollow microspheres; then dissolving 20-40 parts of carbon hollow microspheres, 5-10 titanium salts and 2-6 parts of hexadecyl polyoxyethylene ether in 100 parts of absolute ethyl alcohol, uniformly stirring, then placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal reaction for 6-12h at 120-160 ℃, and then naturally cooling, carrying out suction filtration, washing and drying to obtain titanium compound-containing coated carbon hollow microspheres; finally calcining for 2-4 hours at 500-600 ℃ in air atmosphere to finally obtain the titanium dioxide microsphere with the hollow structure.
The titanium salt is potassium titanate.
The ultraviolet absorption auxiliary agent is 2-chloro-4-nitrophenyloxyethyl methyl cyclohexane.
The preparation method of the titanium dioxide microsphere coated ultraviolet absorption auxiliary filler comprises the following steps: firstly, uniformly mixing 12 parts of nitrophenol and 36 parts of 2-bromoethanol in 60 parts of dichloromethane solvent, and reacting for 2.5 hours at 60 ℃ to generate an aromatic ether compound; then adding 12 parts of 2-chloroethanol, fully and uniformly stirring, then adding 40 parts of titanium dioxide microspheres, reacting for 6 hours at 90 ℃, and generating 2-chloro-4-nitrophenoxy ethyl methyl cyclohexane in the hollow titanium dioxide microspheres; finally washing and vacuum drying to obtain the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler.
The mass ratio of the nitrophenol to the 2-bromoethanol to the 2-chloroethanol is 1:3:1.
The preparation method of the acrylic emulsion comprises the following steps: according to the weight portions, 6 portions of acrylic acid, 6 portions of ethyl acrylate, 40 portions of absolute ethyl alcohol and 4 portions of sodium dodecyl benzene sulfonate are uniformly stirred to form a mixed solution, and then 2 to 4 portions of ammonium persulfate is added to form an acrylic emulsion.
The film forming agent is polyethyl acrylate.
The dispersing agent is polyethylene glycol.
The defoamer is oleate.
The leveling agent is tris (hydroxymethyl) aminomethane.
The preservative is sodium copper ethylenediamine tetraacetate.
The invention also provides a preparation method of the ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall, which is the same as that of the embodiment 1 and is not repeated here.
Example 3
The ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall comprises the following components in parts by weight: 50 parts of titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler, 100 parts of acrylic emulsion, 80 parts of absolute ethyl alcohol, 10 parts of talcum powder, 3 parts of toner, 4 parts of film forming agent, 2 parts of dispersing agent, 2 parts of defoamer, 1 part of flatting agent, 1 part of preservative and 2 parts of hydroxypropyl methyl cellulose. The average size of the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler is 120nm.
The preparation method of the titanium dioxide microsphere comprises the following steps: placing 15 parts of fructose and 4 parts of sodium dodecyl sulfate into 35 parts of mixed solution of water and absolute ethyl alcohol in a volume ratio of 1:1, uniformly stirring, placing into a high-pressure reaction kettle, performing hydrothermal reaction for 20 hours at 200 ℃, cooling, washing, filtering and vacuum drying to obtain carbon hollow microspheres; then, dissolving 35 parts of carbon hollow microspheres, 7 parts of salt and 5 parts of hexadecyl polyoxyethylene ether in 100 parts of absolute ethyl alcohol, uniformly stirring, then placing the mixture in a high-pressure reaction kettle, carrying out hydrothermal reaction for 10 hours at 140 ℃, and then naturally cooling, carrying out suction filtration, washing and drying to obtain titanium compound-containing coated carbon hollow microspheres; finally calcining for 3.5 hours at 550 ℃ in an air atmosphere to finally obtain the titanium dioxide microsphere with the hollow structure.
The titanium salt is prepared by mixing sodium titanate and potassium titanate according to a mass ratio of 1:2.
The ultraviolet absorption auxiliary agent is 2-chloro-4-nitrophenyloxyethyl methyl cyclohexane.
The preparation method of the titanium dioxide microsphere coated ultraviolet absorption auxiliary filler comprises the following steps: firstly, uniformly mixing 16 parts of nitrophenol and 48 parts of 2-bromoethanol in 80 parts of dichloromethane solvent, and reacting for 3 hours at 70 ℃ to generate an aromatic ether compound; then adding 32 parts of 2-chloroethanol, fully and uniformly stirring, adding 50 parts of titanium dioxide microspheres, reacting for 10 hours at 100 ℃, and generating 2-chloro-4-nitrophenoxy ethyl methyl cyclohexane in the hollow titanium dioxide microspheres; finally washing and vacuum drying to obtain the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler.
The mass ratio of the nitrophenol to the 2-bromoethanol to the 2-chloroethanol is 1:3:2.
The preparation method of the acrylic emulsion comprises the following steps: according to parts by weight, 8 parts of acrylic acid, 8 parts of ethyl acrylate, 40 parts of absolute ethyl alcohol and 5 parts of sodium dodecyl benzene sulfonate are uniformly stirred to form a mixed solution, and then 3 parts of ammonium persulfate is added to form an acrylic emulsion.
The film forming agent is polyethyl acrylate.
The dispersing agent is prepared by uniformly mixing cetyl trimethyl ammonium bromide and polyethylene glycol according to the mass ratio of 1:1.
The defoamer is fatty alcohol polyoxyethylene ether.
The leveling agent is polydimethylsiloxane.
The preservative is sodium copper ethylenediamine tetraacetate.
The invention also provides a preparation method of the ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall, which is the same as that of the embodiment 1 and is not repeated here.
Example 4
The ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall comprises the following components in parts by weight: 60 parts of titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler, 110 parts of acrylic emulsion, 90 parts of absolute ethyl alcohol, 12 parts of talcum powder, 6 parts of toner, 5 parts of film forming agent, 3 parts of dispersing agent, 3 parts of defoamer, 2 parts of flatting agent, 2 parts of preservative and 3 parts of hydroxypropyl methyl cellulose. The average size of the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler is 200nm.
The preparation method of the titanium dioxide microsphere comprises the following steps: placing 20 parts of fructose and 6 parts of sodium dodecyl sulfate into 40 parts of mixed solution of water and absolute ethyl alcohol in a volume ratio of 1:1, uniformly stirring, placing into a high-pressure reaction kettle, performing hydrothermal reaction at 250 ℃ for 24 hours, cooling, washing, filtering and vacuum drying to obtain carbon hollow microspheres; then 40 parts of carbon hollow microspheres, 10 titanium salt and 6 parts of hexadecyl polyoxyethylene ether are dissolved in 100 parts of absolute ethyl alcohol, the mixture is stirred uniformly and then placed in a high-pressure reaction kettle for hydrothermal reaction for 12 hours at 160 ℃, and then the carbon hollow microspheres coated with titanium compounds are obtained after natural cooling, suction filtration, washing and drying; finally calcining for 4 hours at 600 ℃ in an air atmosphere to finally obtain the titanium dioxide microsphere with the hollow structure.
The titanium salt is one or a mixture of sodium titanate and potassium titanate.
The ultraviolet absorption auxiliary agent is 2-chloro-4-nitrophenyloxyethyl methyl cyclohexane.
The preparation method of the titanium dioxide microsphere coated ultraviolet absorption auxiliary filler comprises the following steps: firstly, uniformly mixing 20 parts of nitrophenol and 60 parts of 2-bromoethanol in 100 parts of dichloromethane solvent, and reacting for 4 hours at 80 ℃ to generate an aromatic ether compound; then adding 40 parts of 2-chloroethanol, fully and uniformly stirring, then adding 60 parts of titanium dioxide microspheres, reacting for 12 hours at 120 ℃, and generating 2-chloro-4-nitrophenoxy ethyl methyl cyclohexane in the hollow titanium dioxide microspheres; finally washing and vacuum drying to obtain the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler.
The mass ratio of the nitrophenol to the 2-bromoethanol to the 2-chloroethanol is 1:3:2.
The preparation method of the acrylic emulsion comprises the following steps: 10 parts of acrylic acid, 10 parts of ethyl acrylate, 50 parts of absolute ethyl alcohol and 6 parts of sodium dodecyl benzene sulfonate are uniformly stirred to form a mixed solution, and then 4 parts of ammonium persulfate is added to form an acrylic emulsion.
The film forming agent is polyethyl acrylate.
The dispersing agent is polyethylene glycol.
The defoamer is oleate.
The leveling agent is tris (hydroxymethyl) aminomethane.
The preservative is sodium copper ethylenediamine tetraacetate.
The invention also provides a preparation method of the ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall, which is the same as that of the embodiment 1 and is not repeated here.
Example 5
Substantially the same as in example 1, except that the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler was 50 parts.
Example 6
Substantially the same as in example 1, except that the titanium dioxide microsphere coated ultraviolet light absorbing auxiliary composite filler had a part average size of 100nm.
Comparative example 1
Substantially the same as in example 1, except that the coating material was not added with the titanium dioxide microspheres and the ultraviolet absorbing auxiliary composite filler was not coated.
Comparative example 2
Substantially the same as in example 1, except that the titanium dioxide microspheres were not coated with the ultraviolet absorbing auxiliary agent, but were directly used as titanium dioxide microspheres of hollow core structure.
Comparative example 3
Substantially the same as in example 1, except that the ultraviolet absorbing auxiliary agent was not coated with titanium dioxide microspheres, but the ultraviolet absorbing auxiliary agent was directly used.
Comparative example 4
Substantially the same as in example 1, except that the ultraviolet absorbing auxiliary agent was not coated with titanium dioxide, but a mixture of titanium dioxide hollow microspheres and ultraviolet absorbing auxiliary agent of equal mass was separately added in the preparation of the coating material, so that the titanium dioxide microspheres and ultraviolet absorbing auxiliary agent in example 4 were not in a coated structure.
Comparative example 5
Substantially the same as in example 1, except that the composite filler was a solid titanium dioxide microsphere, and thus the ultraviolet absorbing auxiliary agent was not coated.
Characterization test:
The invention adopts a scanning electron microscope to observe the morphology of the titanium dioxide microsphere prepared in the embodiment 1, and can see that the prepared titanium dioxide microsphere has uniform size and good dispersion, so that the titanium dioxide microsphere has excellent heat insulation and ultraviolet resistance. The uniform size distribution ensures that the microspheres can be uniformly distributed in the paint during the coating or wrapping process, thereby providing better heat insulation and ultraviolet resistance.
From fig. 2, which is a microscopic photograph of the titanium dioxide microsphere coated ultraviolet absorbing auxiliary agent in fig. 1, the hollow microsphere structure is visible, which provides a good structural basis for the coated ultraviolet absorbing auxiliary agent, and the coated ultraviolet absorbing auxiliary agent can be obviously seen inside the microsphere structure. In addition, the coating structure increases the contact area between the titanium dioxide microspheres and the ultraviolet absorption auxiliary agent, and further improves the ultraviolet resistance.
FIG. 3 is a phase analysis result of the titanium dioxide microsphere prepared in example 1, and shows that the titanium dioxide microsphere prepared in example 1 contains only a titanium dioxide phase, which means that no impurities or other undesirable substances exist in the preparation process. The pure titanium dioxide microspheres can better exert the heat insulation and ultraviolet resistance, and ensure the high-efficiency function and long-term stability.
Performance test:
the heat insulation performance is one of important indexes of the coating in the application of the building outer wall, and the heat insulation performance of the coating is evaluated mainly by the heat conductivity according to GB/T23987-2009 heat insulation paint for building coating and raw material heat insulation paint thereof, wherein the lower the heat conductivity is, the better the heat insulation performance is. The heat insulation performance of the acrylic resin coating can be evaluated through testing, so that a basis is provided for the application of the acrylic resin coating in the field of paint heat insulation.
Ultraviolet resistance is also one of important properties to be considered in building exterior wall coating materials, and ultraviolet resistance test is carried out by referring to ASTM D4587 standard. The method requires exposing a paint sample to natural sunlight, and evaluating the ultraviolet resistance of the paint by periodically evaluating the indexes such as surface change, color change, adhesion, strength loss and the like. The test results of the paint were classified into five grades according to the degree of change, from excellent to inferior, respectively, 0, 1,2,3 and 4 grades. Wherein 0 represents no change, 1 and 2 represent slight changes, 3 represents moderate changes, and 4 represents severe changes.
The thermal conductivities and ultraviolet resistance levels of the coatings of examples 1 to 6 and comparative examples 1 to 5 are summarized in Table 2.
TABLE 2 thermal conductivity and UV resistance of the coatings of examples 1 to 6 and comparative examples 1 to 5
The main difference between example 1 and comparative example 1 is whether or not the titanium dioxide microsphere coated ultraviolet absorbing auxiliary composite filler is included. This difference results in a significant difference in thermal conductivity and uv resistance rating. In terms of thermal conductivity, since the titanium dioxide microspheres are used in example 1, the thermal conductivity thereof is low, 0.028W/(m·k), and good heat insulating properties are exhibited. In contrast, comparative example 1, in which no titanium dioxide microsphere was used, had a high thermal conductivity of 0.08W/(mK). In terms of ultraviolet resistance, since the titanium dioxide microspheres in example 1 are coated with the ultraviolet absorption auxiliary agent, the ultraviolet resistance thereof is 0, and good ultraviolet resistance is exhibited. In contrast, comparative example 1, in which no titanium dioxide microspheres and no ultraviolet absorbing auxiliary agent were added, had a low ultraviolet resistance rating of only 2. In terms of ultraviolet resistance after 100 days, since the titanium dioxide microsphere in example 1 has a stable coating structure, the ultraviolet resistance is still 0, and the durable ultraviolet resistance protection is shown. Whereas the uv blocking rating of comparative example 1 was reduced to 4 on prolonged exposure.
Comparative example 2 differs significantly from example 1 in the material composition, i.e., whether the titanium dioxide microspheres are coated with an ultraviolet absorbing aid. By comparing the thermal conductivity and the ultraviolet resistance level of the two and combining the related mechanism for in-depth analysis, we draw the following conclusion: comparative example 2 used titanium dioxide microspheres of hollow-core structure, which reduced the thermal conductivity to 0.016W/(mK) below 0.028W/(mK) of example 1. However, since comparative example 2 does not use the coating of the ultraviolet absorbing auxiliary agent, the ultraviolet resistance is poor, the ultraviolet resistance is only 1 grade, and example 1 reaches 0 grade. Furthermore, after a long exposure (100 days), the uv protection rating of comparative example 2 was raised to 2, while example 1 remained unchanged. Therefore, when selecting a coating, we should consider the combination of thermal conductivity and UV resistance, and the combination of the titanium dioxide microspheres and UV absorbing aid used in example 1 is a more desirable choice.
One significant difference between comparative example 3 and example 1 is whether the ultraviolet absorbing aid is coated with titanium dioxide microspheres. By comparing the thermal conductivity and uv-blocking rating of the two, and combining the related mechanism analysis, we draw the following conclusions: since the titanium dioxide microsphere in example 1 has a coating structure, the thermal conductivity is low and is only 0.028W/(m.K), and meanwhile, the titanium dioxide microsphere also provides a certain anti-ultraviolet protection for the material. In contrast, comparative example 3, in which the ultraviolet absorbing auxiliary was directly used, resulted in a higher thermal conductivity, was 0.07W/(mK). The uv protection rating of comparative example 3 was also lower due to the lack of the insulating effect of the titanium dioxide microspheres.
In comparative example 4, the titanium dioxide microspheres and the ultraviolet absorbing aid did not form a coating structure. By conducting an in-depth analysis of the thermal conductivity and uv blocking rating of comparative examples 1 and 4, in combination with the relevant mechanisms, we have reached several important conclusions. First, in terms of thermal conductivity, example 1 exhibited a lower thermal conductivity of 0.028W/(m·k). In contrast, the thermal conductivity of comparative example 4 was slightly higher, reaching 0.032W/(mK). This difference is mainly due to the separate addition of the titanium dioxide microspheres and the uv absorbing aid in comparative example 4, where the filler insulation effect is inferior to the coated filler, resulting in a slight increase in the thermal conductivity of the material. Next, example 1 exhibited excellent ultraviolet resistance, with the ultraviolet resistance rating maintained at 0. The uv rating of example 1 remained stable at level 0 after exposure testing for up to 100 days. However, it is noted that the uv-blocking rating of comparative example 4 was increased to 3 after the same exposure period. The result shows that the titanium dioxide can effectively improve the stability of the ultraviolet-resistant absorption auxiliary agent, and the titanium dioxide hollow microspheres play an important role in enhancing the ultraviolet-resistant stability, so that the overall ultraviolet-resistant capability of the material is improved.
The main difference between comparative example 5 and example 1 is whether the titanium dioxide microspheres are solid or coated with an ultraviolet absorbing aid. In terms of thermal conductivity, the thermal conductivity of example 1 was 0.028W/(mK), whereas the thermal conductivity of comparative example 5 was slightly higher, 0.034W/(mK). This is probably due to the fact that comparative example 5 uses solid titanium dioxide microspheres, which have a slightly higher thermal conductivity than conventional titanium dioxide microspheres, resulting in an increase in the thermal conductivity of the overall material. Example 1 exhibited excellent uv resistance in terms of uv resistance rating of 0. However, the uv-blocking rating of comparative example 5 was only 1, probably because of its relatively weak uv-blocking ability. After 100 days of exposure, the uv rating of example 1 was still 0, while the uv rating of comparative example 5 was increased to 2. This is probably due to the fact that the titanium dioxide microspheres of example 1 are coated with the ultraviolet absorbing auxiliary agent, and can provide ultraviolet protection permanently, so that the ultraviolet protection level is further improved.
In conclusion, the titanium dioxide microsphere coated ultraviolet resistant absorption auxiliary agent provided by the invention shows a remarkable synergistic effect. It not only provides excellent protection against ultraviolet radiation, but also exhibits excellent thermal insulation properties. By uniformly coating the ultraviolet-resistant absorption auxiliary agent on the surface of the titanium dioxide microsphere, the ultraviolet-resistant capability of the material is successfully enhanced, so that the material can more effectively absorb, reflect or scatter ultraviolet rays, and the damage of the ultraviolet rays to objects is remarkably reduced. Meanwhile, the titanium dioxide microspheres have low heat conductivity, can effectively reduce heat conduction, block heat loss and external heat entering, and provide excellent heat insulation effect. The unique coating structure also ensures good durability and permanence, so that the ultraviolet protection effect is stable in long-term use. Therefore, the titanium dioxide microsphere coated ultraviolet resistant absorption auxiliary agent is an ideal choice, and is widely applied to various fields such as paint, plastics and the like. The innovative technology provides strong ultraviolet protection for materials and buildings, obviously improves the weather resistance of the materials and the buildings, and improves the energy efficiency.
Finally, it should be noted that: the above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: all changes in the structure and details of the invention which may be made in the invention are encompassed by the scope of the invention as defined by the claims.
Claims (5)
1. The ultraviolet-resistant acrylic resin heat-insulating coating for the building outer wall is characterized by comprising the following components in parts by weight:
30-60 parts of titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler, 80-110 parts of acrylic emulsion, 40-90 parts of absolute ethyl alcohol, 5-12 parts of talcum powder, 1-6 parts of toner, 2-5 parts of film forming agent, 1-3 parts of dispersing agent, 1-3 parts of defoaming agent, 0.5-2 parts of leveling agent, 0.5-2 parts of preservative and 1-3 parts of hydroxypropyl methyl cellulose;
The average size range of the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler is 50-200 nm;
The preparation method of the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler comprises the following steps: firstly, uniformly mixing 10-20 parts of nitrophenol and 30-60 parts of 2-bromoethanol in 50-100 parts of dichloromethane solvent, and reacting for 2-4 hours at 50-80 ℃ to generate an aromatic ether compound; then adding 10-40 parts of 2-chloroethanol, fully and uniformly stirring, adding 30-60 parts of titanium dioxide microspheres, reacting for 4-12 hours at 80-120 ℃, and generating 2-chloro-4-nitrophenoxy ethyl methyl cyclohexane in the hollow titanium dioxide microspheres; finally washing and vacuum drying to obtain the titanium dioxide microsphere coated ultraviolet absorption auxiliary agent composite filler; the mass ratio of the nitrophenol to the 2-bromoethanol to the 2-chloroethanol is 1:3 (1-2);
The preparation method of the titanium dioxide microsphere comprises the following steps: placing 10-20 parts of fructose and 2-6 parts of sodium dodecyl sulfate into 20-40 parts of mixed solution of water and absolute ethyl alcohol in a volume ratio of 1:1, uniformly stirring, placing into a high-pressure reaction kettle, performing hydrothermal reaction at 160-250 ℃ for 12-24 hours, cooling, washing, filtering and vacuum drying to obtain carbon hollow microspheres; then, dissolving 20-40 parts of carbon hollow microspheres, 5-10 titanium salts and 2-6 parts of hexadecyl polyoxyethylene ether in 100 parts of absolute ethyl alcohol, uniformly stirring, placing in a high-pressure reaction kettle, carrying out hydrothermal reaction at 120-160 ℃ for 6-12 hours, and then naturally cooling, carrying out suction filtration, washing and drying to obtain titanium compound-containing coated carbon hollow microspheres; finally calcining for 2-4 hours at 500-600 ℃ in an air atmosphere to finally obtain the titanium dioxide microsphere with the hollow structure; the titanium salt is one or a mixture of sodium titanate and potassium titanate;
The preparation method of the acrylic emulsion comprises the following steps: according to parts by weight, 4-10 parts of acrylic acid, 5-10 parts of ethyl acrylate, 30-50 parts of absolute ethyl alcohol and 3-6 parts of sodium dodecyl benzene sulfonate are uniformly stirred to form a mixed solution, and then 2-4 parts of ammonium persulfate is added to form an acrylic emulsion.
2. The ultraviolet-resistant acrylic resin heat-insulating coating for building exterior walls according to claim 1, wherein the film forming agent is one or a mixture of more of dodecanol ester and polyethyl acrylate.
3. The ultraviolet resistant acrylic resin heat insulating coating for an exterior wall of a building according to claim 1, wherein the dispersant is polyethylene glycol.
4. The ultraviolet-resistant acrylic resin heat-insulating coating for building exterior walls according to claim 1, wherein the defoamer is fatty alcohol-polyoxyethylene ether.
5. The ultraviolet resistant acrylic resin heat insulating coating for an exterior wall of a building according to claim 1, wherein the leveling agent is polydimethylsiloxane;
The preservative is benzoic acid.
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| CN103589254A (en) * | 2012-08-15 | 2014-02-19 | 贵州柯维建材开发有限公司 | Environment-friendly reflective insulation heat-preserving coating |
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| CN103589254A (en) * | 2012-08-15 | 2014-02-19 | 贵州柯维建材开发有限公司 | Environment-friendly reflective insulation heat-preserving coating |
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