CN114367250B - Polyacrylate polymer @ vanadium dioxide microcapsule, preparation method and application - Google Patents
Polyacrylate polymer @ vanadium dioxide microcapsule, preparation method and application Download PDFInfo
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- CN114367250B CN114367250B CN202210027077.2A CN202210027077A CN114367250B CN 114367250 B CN114367250 B CN 114367250B CN 202210027077 A CN202210027077 A CN 202210027077A CN 114367250 B CN114367250 B CN 114367250B
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- vanadium dioxide
- microcapsule
- polyacrylate polymer
- powder
- deionized water
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 128
- 239000003094 microcapsule Substances 0.000 title claims abstract description 90
- 229920000642 polymer Polymers 0.000 title claims abstract description 61
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 25
- 238000009413 insulation Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 78
- 239000000843 powder Substances 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical class [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 2
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 12
- 239000011521 glass Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 239000011257 shell material Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical compound CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 230000027311 M phase Effects 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Abstract
The invention provides a polyacrylate polymer @ vanadium dioxide microcapsule, a preparation method and application thereof, and belongs to the field of composite materials. The polyacrylate polymer@vanadium dioxide microcapsule provided by the invention has the particle size of 20-100nm. In the preparation process of the polyacrylate polymer@vanadium dioxide microcapsule, the reaction conditions are relatively mild, the environment is protected, the operation is simple, the sample yield is high, the raw materials are cheap and easy to obtain, and the preparation method can be used for mass production. The microcapsule prepared by the invention has narrow particle size distribution range and small size, and can effectively reduce the refraction of light, thereby improving the optical performance. The microcapsule material of the invention is used as an effective component of heat insulation coating, and a coating is constructed on the surfaces of light-transmitting products such as various building walls, glass, organic glass and the like, so that the microcapsule material has good heat insulation and temperature regulation effects, and the heat insulation capability and heat insulation durability of the products are improved.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a polyacrylate polymer @ vanadium dioxide microcapsule, and a preparation method and application thereof.
Background
Research into the intelligent window of vanadium dioxide has been conducted worldwide since the 80 s of the 20 th century, but commercial applications have not yet been realized. Too high a phase transition temperature, an undesirable deep brown-yellow color, lower light transmittance and solar light modulation efficiency are the main reasons that hamper its practical application. In addition, in practical applications, vanadium dioxide eventually oxidizes to vanadium pentoxide without thermochromic properties. The weatherability of vanadium dioxide powder is a great challenge for practical application of smart coatings. And the vanadium dioxide powder prepared by a physical method or a chemical method is more or less agglomerated, so that the regulation and control capability of the vanadium dioxide powder on near infrared light is affected.
In order to solve the oxidation problem of vanadium dioxide, a core-shell structure material which can not only densely coat the vanadium dioxide to prevent the oxidation of the vanadium dioxide, but also improve the dispersibility of the vanadium dioxide and enhance the solar light modulation capability is developed, and is a constantly pursued target.
Disclosure of Invention
The invention aims to provide a polyacrylate polymer @ vanadium dioxide microcapsule, and a preparation method and application thereof, which can effectively solve the problems of easy oxidation, unstable performance and the like of vanadium dioxide in the prior art.
To achieve the above object or other objects, the present invention is achieved by the following technical solutions.
A polyacrylate polymer @ vanadium dioxide microcapsule, wherein the particle size of the microcapsule is 20-100nm.
The method for preparing the polyacrylate polymer @ vanadium dioxide microcapsule comprises the following steps:
(1) Dispersing vanadium dioxide powder in a solvent I, and adding a silane coupling agent under an acidic condition to carry out hydrolysis reaction to obtain modified vanadium dioxide powder;
(2) Dispersing the modified vanadium dioxide powder obtained in the step (1), an emulsifying agent and a dispersing agent in a second solvent under alkaline conditions, and stirring to obtain an emulsified solution;
(3) Adding an initiator and an acrylic monomer into the emulsified solution obtained in the step (2), and adding the initiator and the acrylic monomer into the emulsified solution in the step (N 2 And (3) heating and reacting in the atmosphere, and performing post-treatment to obtain the polyacrylate polymer @ vanadium dioxide microcapsule.
Further, the vanadium dioxide powder is monoclinic (M) phase vanadium dioxide prepared according to the existing one-step ball milling method technology.
Further, the solvent one is selected from one or more of deionized water, ethanol and methanol. Since the silane coupling agent hydrolyzes in deionized water to form a silicon hydroxyl group and the alcohol inhibits excessive hydrolysis, it is preferable that the solvent I in step (1) is a mixed solvent of deionized water and ethanol in a volume ratio of deionized water to ethanol of 1:9.
Further, in the step (1), the vanadium dioxide powder is dispersed in the solvent one, and the concentration of the obtained solution is 10mg/mL.
In the step (1), a silane coupling agent is subjected to hydrolysis reaction to form silicon hydroxyl groups and vanadium dioxide surface hydroxyl groups for condensation, so as to obtain modified vanadium dioxide powder, wherein the silane coupling agent is a coupling agent which contains double bonds and can be copolymerized with acrylic monomers.
Further, the silane coupling agent is selected from one or more of A-171, A-151, KH-A172 and KH 570. Wherein, the hydrolysis speed of A-171 and A-151 is faster, the self-polymerization is easy, the condition requirement is harsh, the hydrolysis speeds of KH-A172 and KH 570 are moderate, and the polymerization with a plurality of monomers is easy. Therefore, preferably, the silane coupling agent is selected from one or two of KH-A172, KH 570.
Further, in the step (2), the solvent II is one or more selected from deionized water, ethanol and methanol, so that the modified vanadium dioxide powder forms a solvent for stabilizing emulsion. Preferably, the second solvent is selected from deionized water. More preferably, the modified vanadium dioxide powder is added to the solvent two in a mass of 1g per 100 ml.
Further, the emulsifier is selected from one or more of Tween 80, span 80 and OP-10. Preferably, the emulsifier is OP-10, OP-10 is used as a hydrophilic emulsifier, and long nonpolar groups of the emulsifier provide excellent lipophilicity, so that the powder is easier to disperse in a water system, and the emulsifier has excellent alkali resistance and can adapt to the alkaline environment of a reaction system.
Further, the dispersing agent is selected from one or more of triethylhexyl phosphoric acid, isobutanol, methyl amyl alcohol and sodium dodecyl sulfate. Preferably, the dispersant is selected from isobutanol.
Further, the initiator is selected from one or more of ammonium persulfate, potassium persulfate, dibenzoyl peroxide and azodiisobutyronitrile. Preferably, the initiator is selected from potassium persulfate, ammonium persulfate and potassium persulfate as water-soluble initiators, while the potassium persulfate has a small half-life and high initiation efficiency.
Further, the acrylic monomer is selected from one of acrylic ester monomer and acrylamide monomer.
Preferably, the acrylic monomer is selected from one of methyl methacrylate, butyl acrylate and hydroxyethyl acrylate. Preferably, the acrylamide monomer is selected from one of N-isopropyl acrylamide, acrylamide and dimethylaminopropyl acrylamide.
Further, in the step (1), the addition amount of the silane coupling agent is 1-10% of the mass of the vanadium dioxide powder. Too few silane coupling agents result in few carbon-carbon double bonds grafted on the surface of the powder, and too many silane coupling agents result in the surface of the powder being coated with multiple layers of coupling agents, which can prevent the copolymerization of the powder and the monomer. Preferably, the addition amount of the silane coupling agent in the step (1) is 3-5% of the mass of the vanadium dioxide powder.
Further, in the step (1), the acidic condition is that the pH is 3 to 6. Preferably, the pH adjustment is performed by acetic acid. More preferably, the acidic condition in the step (1) is that the pH is adjusted to 4-5, and the silane coupling agent can be rapidly hydrolyzed to form silicon hydroxyl.
Further, the hydrolysis reaction temperature in the step (1) is 40-80 ℃ and the reaction time is 4-6 h. Preferably, the hydrolysis reaction in step (1) is carried out at a temperature of 60 ℃.
Further, in the step (2), the alkaline condition is to adjust the pH to 8-10. Preferably, ammonia is used to adjust the pH to 8-10. More preferably, the alkaline conditions in step (2) are such that the pH is adjusted to 9 to 9.5, under which conditions the time for uniform adsorption of the emulsifier on the nanoparticle surface is minimal.
Further, the addition amount of the emulsifier in the step (2) is as follows: 1-10mg of emulsifier is added into 1mL of solvent II. Preferably, in step (2), 1-2mg of emulsifier is added per 1mL of solvent two.
Further, the volume ratio of the dispersant to the solvent II in the step (2) is 0.1% -10%, preferably, the volume ratio of the dispersant to the solvent II in the step (2) is 4% -5%.
Further, in the step (3), the mass ratio of the acrylic monomer to the modified vanadium dioxide powder is (1-4): 1. the shell thickness of the formed microcapsule is determined by the mass of the acrylic acid monomer, so that the particle size of the microcapsule is influenced, the vanadium dioxide powder cannot be completely coated by the acrylic acid monomer with too little mass, the coating of the shell is too thick, the dispersion of the coated powder is not facilitated, and the dimming capability of the coating is weakened when the content of the vanadium dioxide is low. Preferably, in the step (3), the mass ratio of the acrylic monomer to the modified vanadium dioxide powder is (2-4): 1.
further, the initiator in the step (3) is added in an amount of 0.1 to 5% by mass of the acrylic monomer. The amount of initiator added affects the polymerization rate, which affects both the molecular weight and the molecular weight distribution, and preferably the amount of initiator added in step (3) is 2% of the mass of the acrylic monomer.
Further, the temperature of the heating reaction in the step (3) is 50-80 ℃ and the reaction time is 5-7h. Preferably, the temperature of the heating reaction in step (3) is 75 ℃.
Further, the post-treatment in the step (3) includes washing and centrifugation.
The invention also provides an application of the microcapsule in the field of building heat insulation and chemical coating. The microcapsule provided by the invention can be singly or compositely used as a heat insulation component with other components to prepare a heat insulation coating, is used for surfaces of different products, plays roles in heat insulation and temperature adjustment, and saves energy and reduces emission.
Further, the invention also provides a coating material which comprises the polyacrylate polymer@vanadium dioxide microcapsule.
A method of preparing a coating material comprising the steps of: dispersing polyacrylate polymer @ vanadium dioxide microcapsule in organic solvent, adding film forming agent, heating and stirring to form uniform coating.
Further, the concentration of the solution formed by dispersing the polyacrylate polymer @ vanadium dioxide microcapsules into the organic solvent is 5-10mg/mL.
Further, the organic solvent is selected from one of ethanol, tetrahydrofuran, acetone, propyl acetate and butyl acetate. Preferably, the organic solvent is acetone.
Further, the film forming agent is selected from one of polyvinyl alcohol Ding Quanzhi, polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate. Preferably, the film former is polymethyl methacrylate.
Further, the mass volume ratio of the film forming agent to the organic solvent is 50-120mg/mL, namely, the amount of the film forming agent added into each 1mL of the organic solvent is 50-120mg. Preferably, the film former is added in an amount of 90mg per 1mL of organic solvent.
Further, the heating temperature is 40-60 ℃.
In the preparation process of the polyacrylate polymer@vanadium dioxide microcapsule, the silane coupling agent is used for modifying the vanadium dioxide powder, and the acrylic monomer is further polymerized on the surface of the modified powder to form the polyacrylate polymer@vanadium dioxide microcapsule polymer shell layer, so that the polyacrylate polymer@vanadium dioxide microcapsule has the advantages of relatively mild reaction conditions, environment friendliness, safety, simplicity in operation, high sample yield, cheap and easily available raw materials and capability of mass production. The polyacrylate polymer @ vanadium dioxide microcapsule polymer shell material has excellent compatibility with a polymer matrix, so that the dispersibility of vanadium dioxide powder in a solvent and the polymer matrix is greatly improved, the film forming effect is improved, and the prepared coating has excellent uniformity and stability and does not settle after being placed for a long time. The microcapsule of the invention improves the weather resistance (various performances are hardly reduced after being placed for 2 months under the condition that the temperature is 28 ℃ and the humidity is 75%) and the dispersibility of the vanadium dioxide powder, so that the microcapsule has excellent optical modulation capability. Compared with a film prepared by ball milling vanadium dioxide powder, the polyacrylate polymer@vanadium dioxide nano microcapsule prepared by the method has the advantages that after film formation, the uniformity and near infrared light modulation capability of the film are greatly improved; the microcapsule prepared by the invention has narrow particle size distribution range and small size, and can effectively reduce the refraction of light, thereby improving the optical performance. The microcapsule material of the invention is used as an effective component of heat insulation coating, and a coating is constructed on the surfaces of light-transmitting products such as various building walls, glass, organic glass and the like, so that the microcapsule material has good heat insulation and temperature regulation effects, and the heat insulation capability and heat insulation durability of the products are improved.
Drawings
FIG. 1 is a scanning electron microscope image of the vanadium dioxide modified powder prepared in example 1.
FIG. 2 is a scanning electron microscope image of the polyacrylate polymer @ vanadium dioxide microcapsule prepared in example 1.
FIG. 3 is a graph showing the XRD diffraction peaks of the vanadium dioxide modified powder prepared in example 1 before and after two months of standing in an environment at a temperature of 28℃and a humidity of 75%.
FIG. 4 is a graph showing the XRD diffraction peaks of the polyacrylate polymer @ vanadium dioxide microcapsule prepared in example 1 after two months of standing at 28℃and 75% humidity.
FIG. 5 is a TEM diffraction pattern of the polyacrylate polymer @ vanadium dioxide microcapsule prepared in example 1.
FIG. 6 is a statistical chart of particle size of the polyacrylate polymer coated vanadium dioxide spherical microcapsule prepared in example 1.
FIG. 7 is a graph showing the comparison of the optical modulating ability of the polyacrylate polymer coated vanadium dioxide microcapsule coated film prepared in example 1 and the optical modulating ability of the vanadium dioxide coated film prepared by a one-step ball milling method.
Detailed Description
The following specific examples are presented to illustrate the present invention, and those skilled in the art will readily appreciate the additional advantages and capabilities of the present invention as disclosed herein. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. It is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, are generally conducted under conventional conditions or under conditions recommended by the respective manufacturers.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and to which this invention belongs, and any method, apparatus, or material of the prior art similar or equivalent to the methods, apparatus, or materials described in the examples of this invention may be used to practice the invention.
In the embodiment of the invention, a field emission scanning electron microscope (SEM, FEI QUANTAFEG 250) is used for observing the morphology of the polyacrylate polymer @ vanadium dioxide microcapsule; the coating of the polyacrylate polymer @ vanadium dioxide microcapsules was observed using a transmission electron microscope (TEM, JEM 2100, japan); the phase of the vanadium dioxide powder and polyacrylate polymer @ vanadium dioxide microcapsules was observed using X-ray diffraction (XRD, model SmartLabSE, rigaku, japan); the particle size statistics of the polyacrylate polymer @ vanadium dioxide microcapsules were performed by Nanomeasured 1.2 particle size statistical analysis software.
Example 1
(1) Preparing vanadium dioxide modified powder:
1g of vanadium dioxide powder is taken in a 250mL single-neck flask, and added into 100mL of ethanol for ultrasonic treatment for 1h (ultrasonic power is 250W). Preparing deionized water: 100mL of the mixed solution with the volume ratio of ethanol being 1:9 is used for adjusting the pH value to be 4.25 by acetic acid, then 0.05g of silane coupling agent KH-570 is added dropwise, the mixture is stirred and hydrolyzed for 2 hours at 25 ℃, and the mixture is added into a deionized water/ethanol solution system for reaction for 5 hours at 60 ℃. And (3) sequentially centrifugally washing and collecting a product by using deionized water, a mixed solution of deionized water and ethanol, and vacuum drying.
(2) Emulsification of vanadium dioxide modified powder:
1.0g of vanadium dioxide modified powder is taken in a three-neck flask, 100mL of deionized water is added into the three-neck flask, ammonia water is added into the three-neck flask to adjust the pH to be 9.3, 4mL of dispersant isobutanol and 200mg of emulsifier OP-10 are added into the three-neck flask in a dropwise manner, and the three-neck flask is stirred and emulsified for 12h at 25 ℃.
(3) Polymerization of acrylic monomers on the surface of the vanadium dioxide modified powder:
adding 0.08g of potassium persulfate into the vanadium dioxide modified powder emulsion, and adding the mixture into N 2 Under the atmosphere, the temperature is raised to 75 ℃, 4g of methyl methacrylate is added dropwise, and the reaction is carried out for 6 hours. And (3) centrifugally washing the product by using deionized water, ethanol and acetone in sequence, and carrying out vacuum drying to obtain the polyacrylate polymer@vanadium dioxide microcapsule. The particle size of the prepared microcapsule powder is 35-65nm, and the microcapsule powder is spherical.
Example 2
Polyacrylate polymer @ vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (1), the dispersant deionized water is replaced by ethanol, and the obtained vanadium dioxide microcapsule has a particle size of 30-60nm and is spherical.
Example 3
Polyacrylate polymer @ vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (1), KH-570 is replaced by KH-A172, and the obtained vanadium dioxide microcapsule has particle diameter of 40-65nm and spherical shape.
Example 4
Polyacrylate polymer @ vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (1), the mixed solvent used as the hydrolysis of the silane coupling agent is replaced by ethanol, and the obtained vanadium dioxide microcapsule has the particle size of 45-65nm and is spherical.
Example 5
Polyacrylate polymer @ vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (2), the OP-10 is replaced by Span 80, and the obtained vanadium dioxide microcapsule has a particle size of 50-70nm and is spherical.
Example 6
Polyacrylate polymer @ vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (2), the isobutanol is replaced by sodium dodecyl sulfate, and the obtained vanadium dioxide microcapsule has a particle size of 45-70nm and is spherical.
Example 7
Polyacrylate polymer @ vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (3), the potassium persulfate is replaced by ammonium persulfate, and the obtained vanadium dioxide microcapsule has a particle size of 35-60nm and is spherical.
Example 8
Polyacrylate polymer @ vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (3), methyl methacrylate is replaced by butyl acrylate, and the obtained vanadium dioxide microcapsule has a particle size of 40-65nm and is spherical.
Characterization of Performance
1. The vanadium dioxide modified powder and the polyacrylate polymer @ vanadium dioxide microcapsule prepared in the embodiment 1 are respectively subjected to a scanning electron microscope test (using a field emission scanning electron microscope (SEM, FEI QUANTAFEG 250)), and the results are respectively shown in fig. 1 and fig. 2, and as can be seen from fig. 1, the agglomeration phenomenon of the vanadium dioxide powder obtained by the one-step ball milling method is serious, the particle size is 30-40nm, and the morphology is irregular. From FIG. 2, it can be seen that the polyacrylate polymer @ vanadium dioxide microcapsule prepared by the embodiment of the invention is uniformly dispersed, the agglomeration phenomenon is obviously reduced, and the particle size is 35-65nm, and is in a regular sphere shape.
2. The vanadium dioxide modified powder and the polyacrylate polymer @ vanadium dioxide microcapsule prepared in example 1 were placed in an environment with a temperature of 28 ℃ and a humidity of 75% for 2 months, respectively, and the vanadium dioxide modified powder and the polyacrylate polymer @ vanadium dioxide microcapsule were tested, respectively, and as a result, as shown in fig. 3 and fig. 4, respectively, the XRD diffraction patterns (X-ray diffraction (Model SmartLabSE, rigaku, japan)) before and after the vanadium dioxide modified powder was placed in the environment with a temperature of 28 ℃ and a humidity of 75% were measured, and as shown in fig. 4, the XRD diffraction peak patterns before and after the polyacrylate polymer @ vanadium dioxide microcapsule was placed in the environment with a temperature of 28 ℃ and a humidity of 75% were measured, respectively, the XRD diffraction peak patterns (X-ray diffraction (XRD) before and after the vanadium dioxide modified powder was placed in the environment with a temperature of 28 ℃ and a humidity of 75% for 2 months were apparent, and the characteristic peak of M-phase was significantly reduced, and the vanadium dioxide modified powder was significantly changed in the two months after the vanadium dioxide modified powder was placed in the environment with a humidity of 75% were confirmed. After the polyacrylate polymer @ vanadium dioxide microcapsule is placed in an environment with the temperature of 28 ℃ and the humidity of 75% for 2 months, the characteristic peak hardly changes obviously, and the polyacrylate polymer @ vanadium dioxide microcapsule is proved to have almost no change after being placed for two months, so that the polyacrylate polymer @ vanadium dioxide microcapsule prepared by the invention effectively improves the weather resistance of the vanadium dioxide powder and has better stability.
3. Further, the coating condition of the polyacrylate polymer @ vanadium dioxide microcapsule prepared by the invention (transmission electron microscope (TEM, JEM 2100, japan) is observed, and the result is shown in fig. 5, and it can be seen from the graph that the obvious crystal lattice of the vanadium dioxide can be observed in the microcapsule, and the amorphous organic matter is arranged at the edge of the microcapsule, so that the polyacrylate polymer is proved to be coated on the surface of the vanadium dioxide.
4. The particle size statistics of the polyacrylate polymer @ vanadium dioxide microcapsule prepared in example 1 is shown in fig. 6, and it can be seen from fig. 6 that the main particle size of the microcapsule is concentrated in the range of 35-65nm, the particles with the particle size of less than 20nm are uncoated vanadium dioxide and pure polyacrylate polymer microspheres, and the particle size of more than 100nm are multicore microcapsules.
Application example
0.05g of the polyacrylate polymer @ vanadium dioxide microcapsules prepared as described in example 1 was dispersed in 10mL of acetone, 0.9g of PMMA was added as film former and stirred at 50℃until a uniform coating was formed. And (3) coating a layer of coating on the substrate by using a roll coating method, and naturally drying to form a film.
Comparative application example
By the same method as in the application example, 0.05g of vanadium dioxide prepared by a one-step ball milling method was dispersed in 10mL of acetone, 0.9g of PMMA was added as a film forming agent, and stirred at 50℃until a uniform coating was formed. A coating was applied to a substrate by roll coating, and naturally dried to form a film as a comparative application example.
The optical modulation capacities of the films obtained in the application example and the comparative application example were respectively tested by using a UV-Vis spectrometer, the results are shown in fig. 7, and the corresponding analysis results are shown in table 1, and as can be seen from fig. 7 and table 1, the optical modulation capacity (15.56%) of the film coated by the polymethacrylate coated vanadium dioxide microcapsule is far higher than the optical modulation capacity (8.85%) of the film coated by the vanadium dioxide prepared by the one-step ball milling method in the range of 43% -45% of visible light transmittance. This is because the polyacrylate polymer coated vanadium dioxide microcapsule reduces agglomeration among powders, reduces refraction of light, and at the same time, the polymer shell increases compatibility with film forming agent, and improves optical modulation capability of the film.
TABLE 1
Comparative example 1
Polymethyl methacrylate coated vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (1), the adding amount of the siloxane coupling agent KH-570 is reduced to 5mg, and only a very small amount of KH-570 is grafted to the surface of vanadium dioxide under the condition, so that only a small amount of methyl methacrylate is coated on the surface of vanadium dioxide, the agglomeration of the vanadium dioxide cannot be effectively improved, the compatibility with a film forming agent is poor, and the optical modulation capacity of a film after film forming is only 9.02%.
Comparative example 2
Polymethyl methacrylate coated vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (2), the addition amount of OP-10 is reduced to 10mg, under the condition that the solution cannot be fully emulsified, the monomer is difficult to contact with the powder for copolymerization reaction, and the methyl methacrylate is self-polymerized, so that the product obtained by final washing is vanadium dioxide modified powder.
Comparative example 3
Polymethyl methacrylate coated vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (3), the reaction temperature is increased to 85 ℃ at 75 ℃, under the condition, the initiator is rapidly decomposed to generate excessive free radicals so as to cause the methyl methacrylate to burst and gather, and finally the obtained product is gel-like aggregate and can not disperse a coating film.
Comparative example 4
Polyacrylate coated vanadium dioxide microcapsules were prepared as in example 1, except that: in the step (3), the methyl methacrylate as a reaction monomer is replaced by acrylic acid, and the microcapsule obtained under the condition is dispersed in water to form an acidic environment, so that the vanadium dioxide is rapidly dissolved, and the optical modulation capability after coating is reduced by only 1.91%.
The overview shows that the polyacrylate polymer @ vanadium dioxide microcapsule prepared by the method greatly improves the dispersibility of the vanadium dioxide powder in a solvent and a polymer matrix, improves the film forming effect, and has good uniformity and stability, and the prepared coating is not settled after being placed for a long time. After the polyacrylate polymer @ vanadium dioxide nano microcapsule prepared by the method is formed into a film, the uniformity of the film and the near infrared light modulation capability are greatly improved; the microcapsule prepared by the invention has narrow particle size distribution range and small size, and can effectively reduce the refraction of light, thereby improving the optical performance. The microcapsule material of the invention is used as an effective component of heat insulation coating, and a coating is constructed on the surfaces of light-transmitting products such as various building walls, glass, organic glass and the like, so that the microcapsule material has good heat insulation and temperature regulation effects, and the heat insulation capability and heat insulation durability of the products are improved.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (5)
1. A preparation method of polyacrylate polymer @ vanadium dioxide microcapsule is characterized in that the prepared microcapsule has a particle size of 35-65nm and is spherical;
the preparation method comprises the following steps:
(1) Preparing vanadium dioxide modified powder: adding vanadium dioxide powder into ethanol for ultrasonic treatment for 1h; preparing a solvent I, regulating the pH value by acetic acid, then dropwise adding a silane coupling agent, stirring and hydrolyzing 2h at 25 ℃, adding the mixture into ethanol dispersion liquid of vanadium dioxide after the hydrolysis is finished, reacting 4h-6h at 40-80 ℃, sequentially centrifugally washing and collecting a product by using a mixed solution of deionized water, deionized water and ethanol, and vacuum drying to obtain vanadium dioxide modified powder;
(2) Emulsification of vanadium dioxide modified powder: adding deionized water into vanadium dioxide modified powder, adding ammonia water to regulate pH, then dripping dispersant isobutanol and emulsifier OP-10, stirring and emulsifying at 25 ℃ for 12h to obtain an emulsified solution;
(3) Polymerization of acrylic monomers on the surface of the vanadium dioxide modified powder: adding potassium persulfate into the vanadium dioxide modified powder emulsion, and adding the potassium persulfate into N 2 Heating under atmosphere, dropwise adding methyl methacrylate, heating, washing the product with deionized water, ethanol and acetone in turn after the reaction is finished, and drying in vacuum to obtain polyacrylate polymer @ vanadium dioxide microcapsule;
the first solvent in the step (1) is a mixed solvent of deionized water and ethanol, and the volume ratio of the deionized water to the ethanol is 1:9;
in the step (1), the mass ratio of the silane coupling agent to the vanadium dioxide powder is 1-10%;
in the step (1), acetic acid is used for regulating the pH value to 3-6;
in the step (2), ammonia water is used for adjusting the pH value to 8-10;
the addition amount of the emulsifier in the step (2) is as follows: adding 1-10mg of emulsifying agent into every 1mL deionized water;
in the step (2), the volume-mass ratio of deionized water to vanadium dioxide modified powder is 100:1ml/g;
in the step (3), the mass ratio of the methyl methacrylate to the modified vanadium dioxide powder is (1-4): 1, a step of;
in the step (3), the mass ratio of the potassium persulfate to the methyl methacrylate is 0.1-5%;
the volume ratio of the dispersant isobutanol to the deionized water in the step (2) is 0.1-10%;
the heating reaction temperature in the step (3) is 50-80 ℃ and the reaction time is 5-7h.
2. The microcapsule prepared by the preparation method of claim 1 is applied to the field of building heat insulation and chemical coating.
3. A coating material comprising the polyacrylate polymer @ vanadium dioxide microcapsule prepared by the method of claim 1.
4. A method of preparing the coating material of claim 3, comprising the steps of: dispersing polyacrylate polymer @ vanadium dioxide microcapsule in organic solvent, adding film forming agent, heating and stirring to form uniform coating.
5. The method of claim 4, comprising one or more of the following features:
the organic solvent is selected from one of ethanol, tetrahydrofuran, acetone, propyl acetate and butyl acetate;
the film forming agent is one selected from polyvinyl alcohol Ding Quanzhi, polyvinyl alcohol, polyvinylpyrrolidone and polymethyl methacrylate;
the mass volume ratio of the film forming agent to the organic solvent is 50-120 mg/mL;
the heating temperature is 40-60 ℃.
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| CN105218846A (en) * | 2015-09-10 | 2016-01-06 | 昆山博益鑫成高分子材料有限公司 | A kind of microballoon intelligence thermal-insulation window film and preparation method thereof |
| JP2018058734A (en) * | 2016-10-07 | 2018-04-12 | コニカミノルタ株式会社 | Thermochromic vanadium dioxide-containing core-shell particle and production process thereof, and thermochromic film and production process thereof |
| CN112646566A (en) * | 2020-12-01 | 2021-04-13 | 宁波甬安光科新材料科技有限公司 | Based on hollow VO2Preparation method and application of thermochromic film of nano particles |
| CN113174245A (en) * | 2021-04-26 | 2021-07-27 | 济南大学 | Polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105218846A (en) * | 2015-09-10 | 2016-01-06 | 昆山博益鑫成高分子材料有限公司 | A kind of microballoon intelligence thermal-insulation window film and preparation method thereof |
| JP2018058734A (en) * | 2016-10-07 | 2018-04-12 | コニカミノルタ株式会社 | Thermochromic vanadium dioxide-containing core-shell particle and production process thereof, and thermochromic film and production process thereof |
| CN112646566A (en) * | 2020-12-01 | 2021-04-13 | 宁波甬安光科新材料科技有限公司 | Based on hollow VO2Preparation method and application of thermochromic film of nano particles |
| CN113174245A (en) * | 2021-04-26 | 2021-07-27 | 济南大学 | Polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule and preparation method thereof |
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