CN113292680B - Preparation method of intelligent heat-insulating organic glass - Google Patents
Preparation method of intelligent heat-insulating organic glass Download PDFInfo
- Publication number
- CN113292680B CN113292680B CN202110552450.1A CN202110552450A CN113292680B CN 113292680 B CN113292680 B CN 113292680B CN 202110552450 A CN202110552450 A CN 202110552450A CN 113292680 B CN113292680 B CN 113292680B
- Authority
- CN
- China
- Prior art keywords
- pmma
- doped
- organic glass
- slurry
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011521 glass Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 108
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 108
- 239000010936 titanium Substances 0.000 claims abstract description 83
- 239000002002 slurry Substances 0.000 claims abstract description 56
- 239000000843 powder Substances 0.000 claims abstract description 43
- 238000000465 moulding Methods 0.000 claims abstract description 41
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 22
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005341 toughened glass Substances 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 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 claims abstract description 12
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000004513 sizing Methods 0.000 claims abstract description 11
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 11
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 235000011837 pasties Nutrition 0.000 claims abstract description 10
- 238000005266 casting Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- 230000007704 transition Effects 0.000 claims description 15
- 238000002834 transmittance Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002390 adhesive tape Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000009413 insulation Methods 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract 1
- -1 TEP Chemical compound 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002310 reflectometry Methods 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000004984 smart glass Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
Abstract
The invention discloses a preparation method of intelligent heat-insulating organic glass, which comprises the steps of carrying out hydrothermal reaction on vanadium pentoxide, sodium tungstate, titanium sulfate, oxalic acid and urea to obtain W/Ti co-doped VO 2 (M); VO co-doped with W/Ti 2 (M) mixing with TEP, grinding to obtain pasty W/Ti co-doped VO 2 (M) sizing; mixing MMA, TEP, PMMA molding powder with AIBN for dissolution, and polymerizing in a water bath to obtain PMMA molding powder dissolved prepolymer; PMMA molding powder is dissolved into the pre-polymerized material and the VO co-doped with W/Ti 2 (M) mixing the slurry, filtering and vacuum defoaming to obtain PMMA slurry; and placing the transparent PMMA finished plate into a toughened glass mold, grouting PMMA slurry, and intermittently casting PMMA for polymerization to obtain the organic glass. The organic glass can avoid the problems of high manufacturing cost and easy falling, and has the intelligent heat insulation function.
Description
Technical Field
The invention relates to a preparation method of organic glass, in particular to a preparation method of intelligent heat-insulating organic glass, and belongs to the field of organic glass.
Background
VO 2 The application of (M) in smart windows is mainly realized by means of film pasting, coating, interlayer and the like, such as film coating for window glass with set critical temperature successfully developed by Ministry of industrial technology of Japanese industrial technology institute, and smart window with heat-insulating smart glass developed by British scientists. Although the heat island of the city is solved to a different extentThe effect' and the aim of building energy conservation are achieved, but the problems of film falling off, short service life, high cost and the like exist. And VO (Voice) 2 The phase transition temperature of (M) is far higher than the room temperature, the phase transition stability is still to be improved, the visible light transmittance is low, and the application of the phase transition temperature is severely limited in intelligent windows. The literature shows that the valence of the doped cations is greater than or equal to V 4+ In the valence state of (C) to enable VO 2 The phase transition temperature decreases. However, in the current study, VO was doped 2 The doping element used in (M) is mostly a transition metal element. The transition metal ion has coloring effect, VO 2 The visible light transmittance of (M) is lowered to make VO 2 When the phase transition temperature of (M) is reduced to near room temperature, a certain amount of dopant must be added, and VO increases with the dopant content 2 The visible light transmittance of (M) is continuously reduced, the optical, electrical and other performances before and after phase change are also reduced, and the application of the phase change type optical sensor is more limited in intelligent windows. To promote doping VO 2 (M) powder shows good phase change stability and sunlight regulation and control ability when applied to intelligent window, and researchers have developed VO 2 (M) is a core, siO 2 VO with ZnO or the like as shell 2 (M) powder study. Thus, how to mitigate doping VO 2 The problem of the contradiction between (M) powder phase temperature reduction and visible light transmittance reduction and the problem of phase transition temperature reduction and other performance reduction are urgent to be solved.
The organic glass is a transparent material with excellent characteristics of high light transmittance, strong weather resistance, strong plasticity, strong impact resistance, strong corrosion resistance, outstanding insulating effect and the like, and is used for replacing common glass or toughened glass in certain fields. Some countries or regions are also obligatory to use organic glass in certain fields of application, such as the united states and japan, which have imposed regulations in law, and middle and primary schools and kindergarten buildings must use organic glass, which is a trend to replace tempered glass with high-rise buildings, if VO is to be used 2 (M) development of an intelligent insulating organic glass in combination with organic glass is likely to become a new future intelligent window. The university of Sichuan reported nanometer VO for the first time 2 (M) mixing and polymerizing with PMMA prepolymer to obtain the organic glass with infrared intelligent heat insulationResearch reports prove that VO 2 (M) modified organic glass has outstanding heat-insulating properties, but the transmittance of visible light is still to be further improved, which is also VO 2 (M) bottleneck problems in Smart Window applications.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of intelligent heat-insulating organic glass, which can avoid the problems of high manufacturing cost and easy falling of the existing production technologies of film, coating, interlayer and the like of an intelligent window. The prepared intelligent heat-insulating organic glass has good visible light transmittance.
The aim of the invention is achieved by the following technical scheme.
The preparation method of the intelligent heat-insulating organic glass comprises the following steps:
1) W/Ti co-doped VO 2 (M) synthesis and slurry preparation:
W/Ti co-doped VO 2 (M) synthesis:
according to the mass ratio of 2: (0.07-0.30): (0.06-0.20): (0.18-0.20): (130-150) sequentially adding vanadium pentoxide, sodium tungstate, titanium sulfate and urea into oxalic acid aqueous solution under water bath stirring, sealing the mixed system, performing hydrothermal reaction, cooling, standing, pouring supernatant, collecting precipitate, repeatedly washing, drying, and annealing in argon atmosphere to obtain W/Ti co-doped VO 2 (M)；
W/Ti co-doped VO 2 (M) preparation of slurry:
according to the mass ratio (0.5-1): 1 Co-doping the obtained W/Ti with VO 2 (M) mixing with TEP triethyl phosphate, grinding to obtain pasty W/Ti co-doped VO 2 (M) sizing;
2) PMMA slurry preparation:
according to the mass ratio of 100 (15-25) (0-40): (0.05-0.1) mixing and dissolving methyl methacrylate MMA, triethyl phosphate TEP, polymethyl methacrylate PMMA molding powder and azodiisobutyronitrile AIBN, and polymerizing in a water bath to obtain PMMA molding powder dissolved prepolymer;
according to the mass ratio of 100 (0.01 to the whole range)0.5 PMMA molding powder is dissolved in the pre-polymerized material and the VO co-doped with W/Ti 2 (M) mixing the slurry, filtering and vacuum defoaming to obtain PMMA slurry;
3) Intelligent heat-insulating organic glass preparation:
placing the transparent PMMA finished product plate on toughened glass, paving an adhesive tape, covering the toughened glass plate, applying a clamp, pouring PMMA slurry, and producing according to the traditional intermittent casting PMMA polymerization process to obtain the intelligent heat-insulating organic glass.
For the technical scheme, a further preferable scheme of the invention is as follows:
preferably, the W/Ti co-doped VO 2 (M) synthesizing, and sequentially adding the mixture into an oxalic acid aqueous solution with the mass concentration of 0.28-0.30 g/ml under the condition of water bath stirring at 50-60 ℃.
Preferably, the obtained mixed system is sealed and then placed in a drying oven at 185-200 ℃ for hydrothermal reaction for 48-54 h.
Preferably, W/Ti co-doped VO 2 In the synthesis of (M), the precipitate was repeatedly washed 3 times with distilled water and absolute ethanol.
Preferably, W/Ti co-doped VO 2 In the synthesis of (M), after drying for 8-12 h at 50-80 ℃, annealing treatment is carried out for 4-6 h at 600-800 ℃ in a vacuum tube atmosphere furnace protected by argon atmosphere.
Preferably, the paste W/Ti co-doped VO with the fineness of 1-10 mu m is obtained by grinding for 4-6 hours 2 (M) sizing agent.
Preferably, the PMMA slurry is prepared and polymerized in a water bath kettle at the temperature of 75-85 ℃ for 30-60 min to obtain PMMA molding powder dissolved prepolymer.
Preferably, the thickness of the transparent PMMA finished plate is not less than 2mm.
Compared with the prior art, the invention has the beneficial effects that:
1) Synthesized VO 2 (M) is W 6+ And Ti is 4+ Co-doped VO 2 (M), i.e. W/Ti co-doped VO 2 (M) VO doped with W 2 (M) has more excellent optical performance and phase change stability than Ti-doped VO 2 (M) has a lower phase transition temperature, W 6+ And Ti is 4+ Are respectively added byThe added sodium tungstate and titanium sulfate provide the obtained W/Ti co-doped VO 2 (M) is spherical crystal, the phase transition temperature is 30-45 ℃, and the sunlight transmittance/reflectivity under normal temperature condition is higher than that of undoped VO 2 (M) is improved by 5 to 15 percent, the purity is more than 98 percent, and the granularity is less than 1 mu M.
2) VO with W/Ti co-doping 2 (M) mixing with TEP triethyl phosphate, grinding to obtain pasty W/Ti co-doped VO 2 (M) sizing agent, W/Ti co-doped VO 2 (M) grinding into nano particles, which are easier to be stably dispersed in PMMA molding powder dissolved pre-polymerization material and PMMA matrix, and the absorption and dispersion degree of light is small, thus being more beneficial to the transmission of light; the function of TEP is mainly to provide W/Ti co-doped VO 2 (M) grinding medium, more favorable for W/Ti co-doped VO 2 (M) grinding, and can be used as a flame retardant and toughening additive of PMMA to endow PMMA with good flame retardant and rigid-flexible properties.
3) MMA, TEP, PMMA molding powder and AIBN are mixed and dissolved, and PMMA molding powder dissolved and prepolymerized material is obtained by polymerization, so that the PMMA molding powder dissolved material has reactivity, the conversion rate of MMA in PMMA slurry is improved, the polymerization time reaching the corresponding conversion rate of MMA is reduced, the volume shrinkage rate of PMMA slurry is reduced, and the quality of PMMA products is improved; the TEP has the main effects of providing the organic glass with flame retardant property, forming a cosolvent of PMMA molding powder together with MMA, reducing the consumption of MMA, reducing the cost of PMMA production raw materials, playing a good role in PMMA toughening, and being convenient for molding and processing of various different PMMA.
4) PMMA slurry is poured into a toughened glass mold of a built-in transparent PMMA finished product plate to form a double-layer organic glass plate with an intelligent heat insulation layer, so that the production cost of the intelligent heat insulation organic glass is reduced, the optical performance of the intelligent heat insulation organic glass is improved, the intelligent heat insulation organic glass can be endowed with double-color characteristics, and the problems of high manufacturing cost, easy falling and the like existing in the production technologies of film pasting, coating, interlayer and the like of the existing intelligent window are effectively avoided.
Detailed Description
The invention is described in further detail below with reference to examples, but is not intended to be limiting.
The embodiment of the invention provides a preparation method of intelligent heat-insulating organic glass, which comprises the following steps:
1) W/Ti co-doped VO 2 (M) synthesis and slurry preparation:
1a) W/Ti co-doped VO 2 (M) synthesis:
adding 2g of vanadium pentoxide, 0.07-0.30 g of sodium tungstate, 0.06-0.20 g of titanium sulfate and 0.18-0.20 g of urea according to the mass ratio, sequentially adding into 130-150 g of 0.28-0.30 g/ml of oxalic acid aqueous solution under the condition of 50-60 ℃ water bath stirring, transferring the obtained mixed system into a polytetrafluoroethylene reaction kettle, sealing, placing the mixed system into a 185-200 ℃ drying box for hydrothermal reaction for 48-54 h, cooling, standing, pouring supernatant, collecting precipitate, repeatedly washing 3 times with distilled water and absolute ethyl alcohol, drying for 8-12 h at 50-80 ℃, placing into a 600-800 ℃ argon atmosphere protected vacuum tube atmosphere furnace, and annealing for 4-6 h to obtain W/Ti co-doped VO 2 (M)；
1b) W/Ti co-doped VO 2 (M) preparation of slurry:
the W/Ti co-doped VO obtained in step 1 a) is used for preparing the catalyst 2 (M) and TEP triethyl phosphate according to the mass ratio of (0.5-1): 1, grinding for 4-6 h to obtain pasty W/Ti co-doped VO with fineness of 1-10 mu m 2 (M) sizing;
2) PMMA slurry preparation:
2a) Preparing PMMA molding powder by dissolving a prepolymer:
the mass ratio of the refined MMA, TEP, PMMA molding powder to AIBN is 100 (15-25): (0-40): (0.05-0.1) mixing and dissolving, and polymerizing for 30-60 min in a water bath kettle at 75-85 ℃ to obtain PMMA molding powder dissolved prepolymer;
2b) PMMA slurry preparation:
dissolving the PMMA molding powder obtained in the step 2 a) and the W/Ti co-doped VO obtained in the step 1 b) 2 (M) mixing the slurry according to the mass ratio of (0.01-0.5), filtering and vacuum defoaming to obtain the modified polyurethane foam;
3) Intelligent heat-insulating organic glass preparation:
and placing the transparent PMMA finished plate on toughened glass, wherein the thickness of the transparent PMMA finished plate is not less than 2mm. After the adhesive tape is paved, a toughened glass plate is covered, a fixture is arranged, PMMA slurry is poured, and the intelligent heat-insulating organic glass is produced according to the traditional intermittent casting PMMA polymerization process.
The prepared W/Ti co-doped VO 2 (M) is spherical crystal, the phase transition temperature is 30-45 ℃, and the sunlight transmittance/reflectivity under normal temperature condition is higher than that of undoped VO 2 (M) is improved by 5 to 15 percent, the purity is more than 98 percent, and the granularity is less than 1 mu M.
Specific examples are given below to further illustrate the invention.
Example 1
1) W/Ti co-doped VO 2 (M) synthesis and slurry preparation:
W/Ti co-doped VO 2 (M) synthesis:
adding 2g of vanadium pentoxide, 0.20g of sodium tungstate, 0.20g of titanium sulfate and 0.18g of urea according to the mass ratio, sequentially adding into 130g of 0.28g/ml oxalic acid aqueous solution under the condition of 50 ℃ water bath stirring, transferring the obtained mixed system into a polytetrafluoroethylene reaction kettle, sealing, placing into a 200 ℃ drying box for hydrothermal reaction for 50 hours, cooling, standing, pouring supernatant, collecting precipitate, repeatedly washing with distilled water and absolute ethyl alcohol for 3 times, drying at 60 ℃ for 10 hours, placing into a 800 ℃ argon atmosphere protected vacuum tube atmosphere furnace, and annealing for 4 hours to obtain W/Ti co-doped VO 2 (M)；
W/Ti co-doped VO 2 (M) preparation of slurry:
the W/Ti co-doped VO obtained in step 1 a) is used for preparing the catalyst 2 (M) and TEP triethyl phosphate according to the mass ratio of 0.5:1, grinding for 5 hours to obtain pasty W/Ti co-doped VO with fineness of 5 mu m 2 (M) sizing;
2) PMMA slurry preparation:
preparing PMMA molding powder by dissolving a prepolymer:
the mass ratio of the refined MMA, TEP, PMMA molding powder to AIBN is 100:15:30: mixing and dissolving 0.05, and polymerizing in a water bath kettle at 75 ℃ for 40min to obtain PMMA molding powder dissolved prepolymer;
PMMA slurry preparation:
dissolving the PMMA molding powder obtained in the step 2 a) into a prepolymerVO co-doped with W/Ti obtained in step 1 b) 2 (M) mixing the slurry according to the mass ratio of 100:0.5, filtering and vacuum defoaming to obtain the modified alumina;
3) Intelligent heat-insulating organic glass preparation:
and placing the transparent PMMA finished plate on toughened glass, wherein the thickness of the transparent PMMA finished plate is not less than 2mm. After the adhesive tape is paved, a toughened glass plate is covered, a fixture is arranged, PMMA slurry is poured, and the intelligent heat-insulating organic glass is produced according to the traditional intermittent casting PMMA polymerization process.
The prepared W/Ti co-doped VO 2 (M) is spherical crystal, the phase transition temperature is 35 ℃, and the sunlight transmittance/reflectivity is higher than undoped VO under normal temperature condition 2 (M) improves by 15%, the purity is more than 98%, and the granularity is less than 1 μm.
Example 2
1) W/Ti co-doped VO 2 (M) synthesis and slurry preparation:
W/Ti co-doped VO 2 (M) synthesis:
adding 2g of vanadium pentoxide, 0.30g of sodium tungstate, 0.1g of titanium sulfate and 0.20g of urea according to the mass ratio into 140g of 0.3g/ml oxalic acid aqueous solution in sequence under the condition of water bath stirring at 55 ℃, transferring the obtained mixed system into a polytetrafluoroethylene reaction kettle, sealing, placing into a 190 ℃ drying box for hydrothermal reaction for 52h, cooling, standing, pouring supernatant, collecting precipitate, repeatedly washing with distilled water and absolute ethyl alcohol for 3 times, drying at 50 ℃ for 12h, placing into a vacuum tube type atmosphere furnace protected by argon atmosphere at 750 ℃, and annealing for 5h to obtain W/Ti co-doped VO 2 (M)；
W/Ti co-doped VO 2 (M) preparation of slurry:
the W/Ti co-doped VO obtained in step 1 a) is used for preparing the catalyst 2 (M) and TEP triethyl phosphate according to a mass ratio of 1:1, grinding for 4 hours to obtain pasty W/Ti co-doped VO with fineness of 8 mu m 2 (M) sizing;
2) PMMA slurry preparation:
preparing PMMA molding powder by dissolving a prepolymer:
the mass ratio of the refined MMA, TEP, PMMA molding powder to AIBN is 100:20:40:0.08, mixing and dissolving, and polymerizing for 30min in a water bath kettle at 80 ℃ to obtain PMMA molding powder dissolved prepolymer;
PMMA slurry preparation:
dissolving the PMMA molding powder obtained in the step 2 a) and the W/Ti co-doped VO obtained in the step 1 b) 2 (M) mixing the slurry according to the mass ratio of 100:0.3, filtering and vacuum defoaming to obtain the modified alumina;
3) Intelligent heat-insulating organic glass preparation:
and placing the transparent PMMA finished plate on toughened glass, wherein the thickness of the transparent PMMA finished plate is not less than 2mm. After the adhesive tape is paved, a toughened glass plate is covered, a fixture is arranged, PMMA slurry is poured, and the intelligent heat-insulating organic glass is produced according to the traditional intermittent casting PMMA polymerization process.
The prepared W/Ti co-doped VO 2 (M) is spherical crystal, the phase transition temperature is 30 ℃, and the sunlight transmittance/reflectivity is higher than undoped VO under normal temperature condition 2 (M) is improved by 10%, the purity is over 98%, and the granularity is less than 1 mu M.
Example 3
1) W/Ti co-doped VO 2 (M) synthesis and slurry preparation:
W/Ti co-doped VO 2 (M) synthesis:
adding 2g of vanadium pentoxide, 0.10g of sodium tungstate, 0.06g of titanium sulfate and 0.19g of urea according to the mass ratio, sequentially adding into 150g of 0.29g/ml oxalic acid aqueous solution under the condition of water bath stirring at 60 ℃, transferring the obtained mixed system into a polytetrafluoroethylene reaction kettle, sealing, placing into a 185 ℃ drying box for hydrothermal reaction for 54h, cooling, standing, pouring supernatant, collecting precipitate, repeatedly washing with distilled water and absolute ethyl alcohol for 3 times, drying at 70 ℃ for 11h, placing into a 600 ℃ argon atmosphere protected vacuum tube atmosphere furnace, and annealing for 6h to obtain W/Ti co-doped VO 2 (M)；
W/Ti co-doped VO 2 (M) preparation of slurry:
the W/Ti co-doped VO obtained in step 1 a) is used for preparing the catalyst 2 (M) and TEP triethyl phosphate according to the mass ratio of 0.6:1, grinding for 6 hours to obtain pasty W/Ti co-doped VO with fineness of 10 mu m 2 (M) sizing;
2) PMMA slurry preparation:
preparing PMMA molding powder by dissolving a prepolymer:
the mass ratio of the refined MMA, TEP, PMMA molding powder to AIBN is 100:22:20:0.09 is mixed and dissolved, and is polymerized for 50min in a water bath kettle at the temperature of 85 ℃ to obtain PMMA molding powder dissolved prepolymer;
PMMA slurry preparation:
dissolving the PMMA molding powder obtained in the step 2 a) and the W/Ti co-doped VO obtained in the step 1 b) 2 (M) mixing the slurry according to the mass ratio of 100:0.01, filtering and vacuum defoaming to obtain the modified alumina;
3) Intelligent heat-insulating organic glass preparation:
and placing the transparent PMMA finished plate on toughened glass, wherein the thickness of the transparent PMMA finished plate is not less than 2mm. After the adhesive tape is paved, a toughened glass plate is covered, a fixture is arranged, PMMA slurry is poured, and the intelligent heat-insulating organic glass is produced according to the traditional intermittent casting PMMA polymerization process.
The prepared W/Ti co-doped VO 2 (M) is spherical crystal, the phase transition temperature is 45 ℃, and the sunlight transmittance/reflectivity is higher than undoped VO under normal temperature condition 2 (M) improves by 12%, the purity is more than 98%, and the granularity is less than 1 μm.
Example 4
1) W/Ti co-doped VO 2 (M) synthesis and slurry preparation:
W/Ti co-doped VO 2 (M) synthesis:
adding 2g of vanadium pentoxide, 0.07g of sodium tungstate, 0.15g of titanium sulfate and 0.18g of urea according to the mass ratio into 135g of 30g/ml oxalic acid aqueous solution sequentially under the condition of water bath stirring at 53 ℃, transferring the obtained mixed system into a polytetrafluoroethylene reaction kettle, sealing, placing into a 188 ℃ drying box for hydrothermal reaction for 48 hours, cooling, standing, pouring supernatant, collecting precipitate, repeatedly washing with distilled water and absolute ethyl alcohol for 3 times, drying at 80 ℃ for 8 hours, placing into a 700 ℃ argon atmosphere protected vacuum tube type atmosphere furnace, and annealing for 4.5 hours to obtain W/Ti co-doped VO 2 (M)；
W/Ti co-doped VO 2 (M) preparation of slurry:
will step by stepW/Ti co-doped VO obtained in step 1 a) 2 (M) and TEP triethyl phosphate according to the mass ratio of 0.8:1, grinding for 5.5h to obtain pasty W/Ti co-doped VO with fineness of 1 μm 2 (M) sizing;
2) PMMA slurry preparation:
preparing PMMA molding powder by dissolving a prepolymer:
the mass ratio of the refined MMA, TEP, PMMA molding powder to AIBN is 100:25:0.1, mixing and dissolving, and polymerizing for 35min in a water bath kettle at 82 ℃ to obtain PMMA molding powder dissolved prepolymer;
PMMA slurry preparation:
dissolving the PMMA molding powder obtained in the step 2 a) and the W/Ti co-doped VO obtained in the step 1 b) 2 (M) mixing the slurry according to the mass ratio of 100:0.1, filtering and vacuum defoaming to obtain the modified alumina;
3) Intelligent heat-insulating organic glass preparation:
and placing the transparent PMMA finished plate on toughened glass, wherein the thickness of the transparent PMMA finished plate is not less than 2mm. After the adhesive tape is paved, a toughened glass plate is covered, a fixture is arranged, PMMA slurry is poured, and the intelligent heat-insulating organic glass is produced according to the traditional intermittent casting PMMA polymerization process.
The prepared W/Ti co-doped VO 2 (M) is spherical crystal, the phase transition temperature is 42 ℃, and the sunlight transmittance/reflectivity is higher than undoped VO under normal temperature condition 2 (M) improves the purity by 8%, the purity is more than 98%, and the granularity is less than 1 mu M.
Example 5
1) W/Ti co-doped VO 2 (M) synthesis and slurry preparation:
W/Ti co-doped VO 2 (M) synthesis:
adding 2g of vanadium pentoxide, 0.15g of sodium tungstate, 0.18g of titanium sulfate and 0.20g of urea according to the mass ratio into 145g of 0.28g/ml oxalic acid aqueous solution sequentially under the condition of 58 ℃ water bath stirring, transferring the obtained mixed system into a polytetrafluoroethylene reaction kettle, sealing, placing into a 195 ℃ drying box for hydrothermal reaction for 53h, cooling, standing, pouring supernatant, collecting precipitate, repeatedly washing with distilled water and absolute ethyl alcohol for 3 times, drying at 65 ℃ for 9h, and placing into 650 ℃ argon atmosphere for protectionIn a vacuum tube atmosphere furnace, annealing for 5.5h to obtain W/Ti co-doped VO 2 (M)；
W/Ti co-doped VO 2 (M) preparation of slurry:
the W/Ti co-doped VO obtained in step 1 a) is used for preparing the catalyst 2 (M) and TEP triethyl phosphate according to the mass ratio of 0.9:1, grinding for 4.5h to obtain pasty W/Ti co-doped VO with fineness of 3 mu m 2 (M) sizing;
2) PMMA slurry preparation:
preparing PMMA molding powder by dissolving a prepolymer:
the mass ratio of the refined MMA, TEP, PMMA molding powder to AIBN is 100:18:10:0.06, mixing and dissolving, and polymerizing in a water bath kettle at 78 ℃ for 60min to obtain PMMA molding powder dissolved prepolymer;
PMMA slurry preparation:
dissolving the PMMA molding powder obtained in the step 2 a) and the W/Ti co-doped VO obtained in the step 1 b) 2 (M) mixing the slurry according to the mass ratio of 100:0.05, filtering and vacuum defoaming to obtain the modified alumina;
3) Intelligent heat-insulating organic glass preparation:
and placing the transparent PMMA finished plate on toughened glass, wherein the thickness of the transparent PMMA finished plate is not less than 2mm. After the adhesive tape is paved, a toughened glass plate is covered, a fixture is arranged, PMMA slurry is poured, and the intelligent heat-insulating organic glass is produced according to the traditional intermittent casting PMMA polymerization process.
The prepared W/Ti co-doped VO 2 (M) is spherical crystal, the phase transition temperature is 33 ℃, and the sunlight transmittance/reflectivity is higher than undoped VO under normal temperature condition 2 (M) improves the purity by 5%, the purity is more than 98%, and the granularity is less than 1 mu M.
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.
Claims (8)
1. The preparation method of the intelligent heat-insulating organic glass is characterized by comprising the following steps of:
1) W/Ti co-doped VO 2 (M) synthesis and slurry preparation:
W/Ti co-doped VO 2 (M) synthesis:
sequentially adding vanadium pentoxide, sodium tungstate, titanium sulfate and urea into oxalic acid aqueous solution under water bath stirring;
the mass ratio of the vanadium pentoxide to the sodium tungstate to the aqueous solution of the titanium sulfate to the aqueous solution of the urea to the oxalic acid is 2: (0.07 to 0.30): (0.06-0.20): (0.18-0.20): (130-150);
sealing the mixed system, performing hydrothermal reaction, cooling, standing, pouring supernatant, collecting precipitate, repeatedly washing, drying, and annealing in argon atmosphere to obtain W/Ti co-doped VO 2 （M）；
W/Ti co-doped VO 2 (M) preparation of slurry:
according to the mass ratio (0.5-1): 1 Co-doping the obtained W/Ti with VO 2 (M) mixing with TEP triethyl phosphate, grinding to obtain pasty W/Ti co-doped VO 2 (M) sizing;
W/Ti co-doped VO 2 (M) is spherical crystal, the phase transition temperature is 30-45 ℃, and the solar light transmittance under normal temperature condition is higher than that of undoped VO 2 (M) lifting by 5-15%, wherein the purity is more than 98%, and the granularity is less than 1 mu M;
2) PMMA slurry preparation:
according to the mass ratio of 100 (15-25): (10-40): (0.05-0.1) mixing and dissolving methyl methacrylate MMA, triethyl phosphate TEP, polymethyl methacrylate PMMA molding powder and azodiisobutyronitrile AIBN, and polymerizing in a water bath to obtain PMMA molding powder dissolved prepolymer;
according to the mass ratio of 100 (0.01-0.5), PMMA molding powder is dissolved into the pre-polymerized material and the W/Ti co-doped VO 2 (M) mixing the slurry, filtering and vacuum defoaming to obtain PMMA slurry;
3) Intelligent heat-insulating organic glass preparation:
placing the transparent PMMA finished product plate on toughened glass, paving an adhesive tape, covering the toughened glass plate, applying a clamp, pouring PMMA slurry, and producing according to the traditional intermittent casting PMMA polymerization process to obtain the intelligent heat-insulating organic glass.
2. The method for preparing intelligent heat-insulating organic glass according to claim 1, wherein the W/Ti co-doped VO 2 (M) synthesizing, and sequentially adding the mixture into an oxalic acid aqueous solution with the mass concentration of 0.28-0.30 g/ml under the condition of stirring in a water bath at 50-60 ℃.
3. The preparation method of the intelligent heat-insulating organic glass according to claim 1, wherein the obtained mixed system is sealed and then placed in a drying oven at 185-200 ℃ for hydrothermal reaction for 48-54 h.
4. The method for preparing the intelligent heat-insulating organic glass according to claim 1, wherein W/Ti co-doped VO 2 In the synthesis of (M), the precipitate was repeatedly washed 3 times with distilled water and absolute ethanol.
5. The method for preparing the intelligent heat-insulating organic glass according to claim 1, wherein W/Ti co-doped VO 2 In the synthesis of (M), after drying for 8-12 hours at 50-80 ℃, annealing treatment is carried out for 4-6 hours at 600-800 ℃ in a vacuum tube atmosphere furnace protected by argon atmosphere.
6. The preparation method of the intelligent heat-insulating organic glass according to claim 1, wherein the PMMA slurry is prepared and polymerized in a water bath kettle at 75-85 ℃ for 30-60 min to obtain PMMA molding powder dissolved prepolymer.
7. The method for preparing intelligent heat-insulating organic glass according to claim 1, wherein the thickness of the transparent PMMA finished plate is not less than 2mm.
8. An intelligent insulating organic glass made by the method of any one of claims 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110552450.1A CN113292680B (en) | 2021-05-20 | 2021-05-20 | Preparation method of intelligent heat-insulating organic glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110552450.1A CN113292680B (en) | 2021-05-20 | 2021-05-20 | Preparation method of intelligent heat-insulating organic glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113292680A CN113292680A (en) | 2021-08-24 |
| CN113292680B true CN113292680B (en) | 2024-03-01 |
Family
ID=77323205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110552450.1A Active CN113292680B (en) | 2021-05-20 | 2021-05-20 | Preparation method of intelligent heat-insulating organic glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113292680B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700909A (en) * | 2009-11-25 | 2010-05-05 | 中国科学技术大学 | Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method |
| CN102181115A (en) * | 2011-02-12 | 2011-09-14 | 台州艾斐建材有限公司 | Polymethyl methacrylate product and preparation method thereof |
| CN102729381A (en) * | 2011-03-29 | 2012-10-17 | 邹建仁 | Method for manufacturing organic glass with double layers and double colors |
| CN107603102A (en) * | 2017-09-15 | 2018-01-19 | 四川大学 | Lucite and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014505651A (en) * | 2011-01-21 | 2014-03-06 | 中国科学院上海硅酸塩研究所 | Doped vanadium dioxide powder, dispersions and their production and application |
-
2021
- 2021-05-20 CN CN202110552450.1A patent/CN113292680B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700909A (en) * | 2009-11-25 | 2010-05-05 | 中国科学技术大学 | Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method |
| CN102181115A (en) * | 2011-02-12 | 2011-09-14 | 台州艾斐建材有限公司 | Polymethyl methacrylate product and preparation method thereof |
| CN102729381A (en) * | 2011-03-29 | 2012-10-17 | 邹建仁 | Method for manufacturing organic glass with double layers and double colors |
| CN107603102A (en) * | 2017-09-15 | 2018-01-19 | 四川大学 | Lucite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吕维忠等.钨-氟共掺杂二氧化钒的水热法制备及表征.《深圳大学学报理工版》.2015,第32卷(第4期),385-389. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113292680A (en) | 2021-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101906261B (en) | Thermal insulating glass coating with high leveling property | |
| CN107267011A (en) | A kind of coating with heat insulating reflecting function and preparation method thereof | |
| WO2015055115A1 (en) | Transparent flame-retardant thermal-insulating uv-blocking polymer composite film, preparation method and uses thereof | |
| CN107779024A (en) | A kind of heat-preservation building paint containing nanoparticle and preparation method thereof | |
| CN102040797A (en) | Graphene/TiO2-based near-infrared/ultraviolet radiation resistant polymer composite film and preparation method thereof | |
| CN110467878B (en) | Long-acting heat-insulating and cooling coating for energy-saving building and preparation method thereof | |
| CN108410283A (en) | A kind of aqueous reflective heat-insulation paint and preparation method thereof | |
| CN105129856A (en) | Resol-assisted synthetic large aperture ordered mesopore metallic oxide material and preparation method of material | |
| CN105565660A (en) | High-performance aluminosilicate glass primarily made from red mud and preparation method of high-performance aluminosilicate glass | |
| CN113292680B (en) | Preparation method of intelligent heat-insulating organic glass | |
| CN108084860B (en) | Environment-friendly heat-insulating coating and preparation method thereof | |
| CN103897577B (en) | glass coating and preparation method thereof | |
| CN101418155A (en) | Sun screen and heat insulation nano composite material for reflecting infrared and preparation method thereof | |
| CN110818338A (en) | Outdoor low-heat-absorption inorganic artificial stone plate and preparation method thereof | |
| CN108912871B (en) | Preparation method of water-based transparent heat-insulating glass coating | |
| CN102260442A (en) | Water-based solar heat radiation reflective paint and preparation process thereof | |
| CN114735944B (en) | Optical glass coated with nano material on surface and preparation method thereof | |
| CN110615646B (en) | High-strength light slurry and preparation method thereof | |
| CN113480332A (en) | Heat-preservation and heat-insulation building material and preparation method thereof | |
| CN111303771A (en) | Graphene water-based paint and processing technology thereof | |
| CN108690308A (en) | A kind of novel organic glass and preparation method thereof | |
| CN108314328B (en) | Preparation method of high-strength composite glass | |
| CN1224585C (en) | Photoselective Ce/Fe film and its preparation method | |
| CN114561115B (en) | VOC-free nano transparent heat-insulating coating and preparation method thereof | |
| CN115594227B (en) | Inorganic yellow high-entropy pigment with high near infrared reflection performance and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240125 Address after: Room 102, 1st Floor, Office Building, Dazhang Industrial Park, Lianjiangkou Town, Yingde City, Qingyuan City, Guangdong Province, China (Office Only) Applicant after: The City Hongtai Glass Co.,Ltd. Country or region after: China Address before: 710046 Dongguan Xiaoguanzi, Hantai District, Hanzhong City, Shaanxi Province Applicant before: Shaanxi University of Technology Country or region before: China |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |