CN114934737B - Preparation method of photo-thermal double-adjustment intelligent glass - Google Patents
Preparation method of photo-thermal double-adjustment intelligent glass Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000003756 stirring Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000017 hydrogel Substances 0.000 claims abstract description 41
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 38
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002390 adhesive tape Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920002678 cellulose Polymers 0.000 claims abstract description 15
- 239000001913 cellulose Substances 0.000 claims abstract description 15
- 238000004090 dissolution Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- -1 naphthopyran compound Chemical class 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 41
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 11
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 11
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 10
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 9
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 9
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 9
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 9
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 9
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 8
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 3
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical class C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000005329 float glass Substances 0.000 claims description 3
- MCQOWYALZVKMAR-UHFFFAOYSA-N furo[3,4-b]pyridine-5,7-dione Chemical compound C1=CC=C2C(=O)OC(=O)C2=N1 MCQOWYALZVKMAR-UHFFFAOYSA-N 0.000 claims description 3
- KFKMGUPDWTWQFM-UHFFFAOYSA-N furo[3,4-c]pyridine-1,3-dione Chemical compound N1=CC=C2C(=O)OC(=O)C2=C1 KFKMGUPDWTWQFM-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- GBBPFLCLIBNHQO-UHFFFAOYSA-N 5,6-dihydro-4h-cyclopenta[c]furan-1,3-dione Chemical compound C1CCC2=C1C(=O)OC2=O GBBPFLCLIBNHQO-UHFFFAOYSA-N 0.000 claims description 2
- IZJDCINIYIMFGX-UHFFFAOYSA-N benzo[f][2]benzofuran-1,3-dione Chemical compound C1=CC=C2C=C3C(=O)OC(=O)C3=CC2=C1 IZJDCINIYIMFGX-UHFFFAOYSA-N 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 102
- 230000000903 blocking effect Effects 0.000 description 29
- 238000002834 transmittance Methods 0.000 description 25
- 238000005303 weighing Methods 0.000 description 19
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 238000007789 sealing Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 238000009413 insulation Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 9
- 230000001376 precipitating effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 7
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
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Classifications
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
- E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
- E06B3/67—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light
- E06B3/6715—Units comprising two or more parallel glass or like panes permanently secured together characterised by additional arrangements or devices for heat or sound insulation or for controlled passage of light specially adapted for increased thermal insulation or for controlled passage of light
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
- E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
- E06B3/6621—Units comprising two or more parallel glass or like panes permanently secured together with special provisions for fitting in window frames or to adjacent units; Separate edge protecting strips
- E06B3/6625—Units comprising two or more parallel glass or like panes permanently secured together with special provisions for fitting in window frames or to adjacent units; Separate edge protecting strips molded on the edges
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
- E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
- E06B3/677—Evacuating or filling the gap between the panes ; Equilibration of inside and outside pressure; Preventing condensation in the gap between the panes; Cleaning the gap between the panes
- E06B3/6775—Evacuating or filling the gap during assembly
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B10/00—Integration of renewable energy sources in buildings
- Y02B10/20—Solar thermal
Landscapes
- Engineering & Computer Science (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a preparation method of photo-thermal double-regulation intelligent glass, which comprises the following steps: adding naphthopyran compound NP into tetrahydrofuran for dissolution, adding anhydride, heating, refluxing and stirring for full reaction to obtain compound NP-COOH; adding cellulose, compound NP-COOH and DMAP into tetrahydrofuran for full dissolution, then dropwise adding tetrahydrofuran solution of DCC into the system under ice bath, stirring for reaction after the dropwise adding is finished, and then stirring for reaction at room temperature to obtain compound NP-celllose; heating, stirring and mixing a compound NP-cellulose with pure water, stirring and reacting at room temperature, and centrifuging to obtain a functional hydrogel; the four sides of the glass are well adhered by the adhesive tape, a cavity is formed between the two pieces of glass, a gap is reserved, the functional hydrogel is filled and injected between the two pieces of glass from the gap, and then the adhesive tape is taken to seal the gap to obtain the photo-thermal double-adjustment intelligent glass. The invention has simple process and low cost.
Description
Technical Field
The invention belongs to the technical field of functional glass preparation, and particularly relates to a preparation method of photo-thermal double-regulation intelligent glass.
Background
The intelligent material is the material with intelligent characteristics of sensing environmental (including internal environment and external environment), analyzing, processing and judging the stimulus, and taking certain measures to perform moderate response. The intelligent material is a fourth generation material after natural materials, synthetic high polymer materials and artificial design materials, is one of important development directions of modern high new materials, supports the development of future high new technologies, gradually eliminates the limit of functional materials and structural materials in the traditional sense, and realizes structural functionalization and functional diversification.
In the building industry, the intellectualization of building materials is also gradually advanced into the heart of people. Among them, the energy consumption of the building caused by the glass door and window is quite large, and especially the problems of transmittance and absorptivity when sunlight is involved are more attractive to many researchers. The intelligent glass at present mainly comprises photochromic glass, and the studied photochromic glass mainly comprises thermochromic glass, electrochromic glass, photochromic glass and gasochromic glass.
For single thermochromic glass, the color change critical temperature of the common thermochromic glass is higher, and the thermochromic glass can change color and insulate heat in extremely hot weather, because the hydrogel thermal change material becomes opaque after being changed in color, so that the transmittance is affected, and if the color change temperature is set to be lower, the look and feel of a user is often affected. This results in thermochromic glasses being useless in hotter weather; for electrochromic glass, the electrochromic glass can achieve the effect of color changing and heat insulation by electrifying, which is against the original purpose of green energy saving; for single photochromic glass, the performance is good in the case of hot weather, but the heat insulation effect reaches the limit in the case of particularly hot weather, so that the heat insulation effect is poor; the color-changing device in the gas-induced color-changing glass has simple system structure, but has relatively high preparation cost in practical application and is not easy for mass production.
In a word, the limitation of the single adjusting method is large, and the manufactured intelligent glass is easy to cause various problems such as poor heat insulation effect, violation of energy-saving principle, poor light transmittance and the like.
Disclosure of Invention
The invention aims to provide a preparation method of photo-thermal double-regulation intelligent glass.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a preparation method of photo-thermal double-regulation intelligent glass, which comprises the following steps:
firstly, adding naphthopyran compound NP into tetrahydrofuran for dissolution, adding anhydride, heating, refluxing and stirring for full reaction to obtain compound NP-COOH;
the molar ratio of the naphthopyran compound NP to the anhydride is 1 (0.5-5); preferably 1:2;
the structure of the naphthopyran compound NP is shown as follows:
wherein R is 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy.
The anhydride is at least one of succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride, 1-cyclopentene-1, 2-dicarboxylic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, 2, 3-pyridine dicarboxylic anhydride, pyridine-3, 4-dicarboxylic anhydride, isatoic anhydride, 1, 8-naphthalene dicarboxylic anhydride and 2, 3-naphthalene dicarboxylic anhydride;
adding cellulose and the compound NP-COOH and DMAP prepared in the first step into tetrahydrofuran for full dissolution, then dropwise adding a tetrahydrofuran solution of DCC into the system under ice bath, stirring for reaction after the dropwise adding is finished, and then stirring for reaction at room temperature to obtain the compound NP-cellulose;
the cellulose is at least one selected from methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose and hydroxyethyl methylcellulose;
thirdly, heating, stirring and mixing the compound NP-cellulose prepared in the second step with pure water, then stirring and reacting at room temperature, and centrifuging to obtain the functional hydrogel; the mass ratio of the NP-cellulose prepared in the second step to the pure water is 1 (30-65);
fourthly, sticking the adhesive tape on four sides of the glass to form a cavity between the two pieces of glass, reserving a gap, filling the functional hydrogel between the two pieces of glass from the gap, and then taking the adhesive tape to seal the gap to obtain the photo-thermal double-regulation intelligent glass.
The molar quantity of the naphthopyran compound NP and the volume ratio of tetrahydrofuran in the first step are 1mmol (5-20 mL).
Preferably, in the first step, naphthopyrans NP, R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, -CH 3 、-C 2 H 5 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-OCH 3 、-OC 2 H 5 、-OCH 2 CH 2 CH 3 、-OCH(CH 3 ) 2 、-O CH 2 CH 2 CH 2 CH 3 。
In the first step, the structure of the naphthopyran compound NP is selected from one of the following structures:
the structure of the compound NP-COOH is shown as follows:
wherein R is 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy.
R is selected from- (CH) 2 )n-、-CH＝CH-、
n is an integer of 1 to 6.
Preferably, the compound NP-COOH, R in said first step 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, -CH 3 、-C 2 H 5 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-OCH 3 、-OC 2 H 5 、-OCH 2 CH 2 CH 3 、-OCH(CH 3 ) 2 、-O CH 2 CH 2 CH 2 CH 3 。
R is selected from-CH 2 -、-CH＝CH-、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 CH 2 CH 2 -、
In the first step, the temperature of the heating reflux stirring full reaction is 40-80 ℃ and the time is 1-12 h.
In the first step, the compound NP-COOH is selected from the following structures:
in the second step, the mass ratio of the compound NP-COOH prepared in the first step to cellulose is 1 (0.1-2).
In the second step, the molar ratio of the compound NP-COOH to DMAP prepared in the first step is 1 (0.8-2), preferably 1:1.2.
In the second step, the molar ratio of the compound NP-COOH to DCC prepared in the first step is 1 (0.5-3).
In the second step, the molar quantity of the compound NP-COOH prepared in the first step and the volume ratio of tetrahydrofuran are 1mmol (5-20 mL).
In the second step, the concentration of the tetrahydrofuran solution of DCC is 0.5-1.2mmol/mL.
And in the second step, stirring and reacting for 1-3 hours after the dripping is finished.
And in the second step, the reaction is continuously stirred at room temperature for 1-24 hours.
The temperature of heating, stirring and mixing in the third step is 60-80 ℃ and the time is 5-10 h.
And in the third step, stirring and reacting at room temperature for 5-10 h.
The distance between the two glass sheets in the fourth step is 0.18-0.23 mm, preferably 0.20mm.
The fourth step is that the amount of the functional hydrogel filled between two pieces of glass is as follows: every 1m 2 The glass infusion functional hydrogel is 0.8-1.2 kg, preferably 1.0kg.
The dimensions of the glass: float glass having a length and width of 10cm×10cm and a thickness of 3mm.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
compared with single-adjustment intelligent glass, the photo-thermal double-adjustment intelligent glass provided by the invention can be flexibly and automatically adjusted according to the change of weather, and the infrared blocking rate is about 12% when the weather is cold, so that the solar heat can be hardly blocked from entering a room; when the weather is hot, the infrared blocking rate can reach more than 80%, so that most heat is blocked from entering a room, and the indoor heating in winter and cooling in summer are truly realized; due to the characteristics of the photochromic material, the ultraviolet light can be absorbed to achieve the effect of changing color, so that the ultraviolet light can be effectively blocked, and the damage of the ultraviolet light to human bodies is reduced; the process is simple, the cost is low, and the industrial production is easy; pure water is used as a solvent, and the whole process is free from using excessive organic reagents, so that the environment is protected; the indoor temperature can be effectively regulated, the use of electric appliances such as an air conditioner is reduced, and the energy-saving problem is solved from the source.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The principle of the photo-thermal double-regulation intelligent glass of the invention is that: the thermal response functional hydrogel prepared from cellulose has special properties, and can be colorless and transparent at the temperature of less than 50 ℃ and white and opaque at the temperature of more than 50 ℃, so that the glass can effectively block infrared radiation and thermal radiation, and the effect of isolating outdoor heat is achieved. The polymer composed of the photochromic compound can be colorless and transparent under the condition of no ultraviolet light or sunlight irradiation or weaker sunlight, and can be changed into colored and transparent under the condition of sunlight irradiation, so that the effects of effectively blocking high-energy ultraviolet light and isolating part of heat are achieved, and the blocking effect can be optimal in noon or summer. The hydrogel with general thermal response has higher phase transition temperature, is opaque after phase transition and has great access to actual application scenes; the technical scheme of the photochromic composition mainly isolates ultraviolet rays, and has no high-efficiency blocking effect on most heat radiation transmission.
According to the invention, the thermal hydrogel and the naphthopyran photochromic compound are combined and applied to the glass by a chemical method, so that the intelligent glass can have high visible light transmittance and low infrared blocking rate at low temperature, has higher visible light transmittance and higher infrared blocking rate at high temperature, and can have low visible light transmittance and higher infrared blocking rate when the temperature is higher and reaches the hydrogel color changing temperature.
The intelligent glass of the invention comprises the following concrete components: under the condition of cloudy days, the air temperature is not too high, and the glass does not influence the transmission of light rays and the transmission of heat, and the glass is represented as common glass. Under the condition of sunny days, when the air temperature is below 30 ℃, the glass is light-colored and transparent, and heat is basically not blocked from entering a colder room; when the temperature is 30-38 ℃, the glass is dark transparent, and can effectively block heat; when the temperature is above 38 ℃, the glass is dark and opaque, and can block a large amount of heat. In general, the technical scheme of the invention combines a photo-thermal dual-response method to intelligently adjust the ultraviolet blocking rate and the infrared heat radiation blocking rate of the glass so as to achieve the effect of indoor warmness in winter and coldness in summer and reduce carbon emission and energy use.
The glass used in the examples of the present invention was purchased from Shanghai Yuntian glass Co., ltd., and was float glass (hereinafter referred to as glass) having a length and width of 10 cm. Times.10 cm and a thickness of 3 mm; the adhesive tape used was purchased from Songgangan Antaixing adhesive products company, shenzhen Baoan district, 2mm wet laminated glass edge sealing adhesive tape (hereinafter referred to as adhesive tape).
Abbreviations used in the examples of the present invention: DMAP: 4-dimethylaminopyridine, DCC: dicyclohexylcarbodiimide.
Example 1
(1) 3, 3-diphenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 1 (5 mmol,2.20 g) (synthetic method is referenced by Qian Zhao, yanhua Yang, YInxiang Duan, xian Tao, YIngzheng Shen. Synthesis andPhotochromic Properties of naphthopyran symmetrical polyaryl subsystems, chem. Heterocycl. Com. 2018.) in 50mL tetrahydrofuran, succinic anhydride (10 mmol,1.00 g) was added to the solution, the reaction was carried out under reflux with heating in an oil bath at 60℃for 8h, cooled to room temperature, extracted with 200mL of aqueous HCl solution and 200mL of toluene, the toluene layer was washed with hot water at 60℃until it became neutral, and 1.8g of compound NP was obtained after rotary evaporation of the solvent from the toluene layer 1 -COOH， 1 H NMR(300MHz，CDCl 3 ):12.18(s,-COOH),8.56-8.70(m,1H)，8.22-8.28(m,2H)，7.74(d,1H)，7.57(t,1H)，7.28-7.39(m,13H)，7.04(s,1H)，6.38(d,1H)，6.58(d,1H)，2.71(t,2H)，2.52(t,2H)；HRMS(ESI,m/z):[M+H] + calcd for(C 36 H 26 O 5 ) 539.1853; found,539.1861, equation:
(2) 1.30g of hydroxymethyl cellulose (HMC) with molecular weight of 100000 and NP 1 Adding (1.35 g, 2.5 mmol) COOH and DMAP into 25mL tetrahydrofuran for fully dissolving, then dropwise adding 5mL of 0.8mmol/mL DCC tetrahydrofuran solution into the system under ice bath, stirring for 2h after the dropwise adding, stirring at room temperature again for continuous stirring for 24h, slowly pouring the reaction solution into 60 ℃ hot water with stirring after the reaction is finished, precipitating purple floccules, filtering, washing 3 times with 60 ℃ hot water, and vacuum drying to obtain 1.23g compound NP 1 -HMC；
(3) 1.2g NP 1 HMC was added to the flask, 60g of pure water was added thereto, stirred at 70℃for 6 hours, stirred at room temperature for 8 hours, and centrifuged to obtain 61.2g of a functional hydrogel.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
The specific test method comprises the following steps: the photo-thermal double-regulation intelligent glass is placed for 10 minutes, then is detected and recorded by an on-forest LS183 transmittance detector, the operation is repeated for a plurality of times in different days for detection, and the average value of the detection is filled in the table 1.
Example 2
(1) 3-methylphenyl-3' -phenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 2 (5 mmol,2.27 g) was dissolved in 50mL tetrahydrofuran, maleic anhydride (10 mmol,0.98 g) was added to the solution, the mixture was heated in an oil bath at 60℃under reflux and stirred for 8 hours, cooled to room temperature, 200mL of 10mol/L aqueous HCl and 200mL of toluene were added to extract, the toluene layer was washed with hot water at 60℃until it became neutral, and 1.9g of compound NP was obtained by rotary evaporation of the solvent from the toluene layer 2 -COOH， 1 HNMR(300MHz,CDCl 3 ):16.35(s,-COOH),8.68(d,1H)，8.23-8.28(m,2H)，7.74(d,1H)，7.57(t,1H)，7.23-7.39(m,10H)，7.09(d,1H)，7.04(s,1H)，6.58(d,1H)，6.39(d,1H)，6.27-6.34(dd,2H)，7.57(t,1H)；HRMS(ESI,m/z):[M+H] + calcd for(C 37 H 26 O 5 ) 551.1853; found,551.1845, equation:
(2) 1.30g of hydroxymethyl cellulose (HMC) with molecular weight of 100000 and NP 2 Adding (1.38 g, 2.5 mmol) COOH and DMAP (3 mmol,0.37 g) into 25mL tetrahydrofuran for complete dissolution, then dropwise adding 5mL of 0.8mmol/mL DCC tetrahydrofuran solution into the system under ice bath, stirring after the addition, reacting for 2h, then stirring at room temperature for further reaction for 24h, slowly pouring the reaction solution into 60 ℃ hot water while stirring after the reaction is completed, precipitating purple floccules, filtering, washing 3 times with 60 ℃ hot water, and vacuum drying to obtain 1.25g compound NP 2 -HMC；
(3) Weighing NP 2 HMC (1.2 g) was added to the flask, 60g of pure water was added thereto, stirred at 70℃for 6 hours, and stirred at room temperature for 8 hours again, and after centrifugation, 61.2g of a functional hydrogel was obtained.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 3
(1) 3,3' -dimethylphenyl-3, 13-dihydronaphthopyran [2,1-f ]]-13-ol NP 3 (5 mmol,2.34 g) was dissolved in 50mL tetrahydrofuran and the glutaryl is weighedAnhydride (10 mmol,1.14 g) is added into the solution, the mixture is heated in an oil bath at 60 ℃ for reflux and stirring reaction for 8 hours, the mixture is cooled to room temperature, 200mL of 10mol/L HCl aqueous solution and 200mL of toluene are added for extraction, the toluene layer is washed with hot water at 60 ℃ until the toluene layer is neutral, and 1.9g of compound NP can be obtained after the toluene layer is rotationally evaporated to obtain the solvent 3 -COOH， 1 HNMR(300MHz,CDCl 3 ):12.01(s,-COOH),8.68(d,1H)，8.22-8.28(m,2H)，7.74(d,1H)，7.57(t,1H)，7.29-7.39(m,3H)，7.23(d,4H)，7.09(d,4H)，7.04(s,1H)，6.58(d,1H)，6.39(d,1H)，2.29-2.36(m,4H)，2.19(s,6H)，2.09-2.17(m,2H)；HRMS(ESI,m/z):[M+H] + calcd for(C 39 H 32 O 5 ) 581.2323; found,581.2335, equation:
(2) Weighing 1.30g of hydroxyethyl cellulose (HEC) with molecular weight of 100000 and NP 3 Adding (1.45 g, 2.5 mmol) COOH and DMAP (3 mmol,0.37 g) into 25mL tetrahydrofuran for complete dissolution, then dropwise adding 5mL of 0.8mmol/mL DCC tetrahydrofuran solution into the system under ice bath, stirring after the addition, reacting for 2h, then stirring at room temperature for further reaction for 24h, slowly pouring the reaction solution into 60 ℃ hot water while stirring after the reaction is completed, precipitating purple floccules, filtering, washing 3 times with 60 ℃ hot water, and vacuum drying to obtain 1.3g compound NP 3 -HEC；
(3) Weighing NP 3 HEC (1.2 g) was added to the flask, and 60g of pure water was added thereto, and stirred at 70℃for 6 hours, at room temperature for 8 hours, and centrifuged to obtain 61.2g of a functional hydrogel.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 4
(1) 3-ethylphenyl-3' -phenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 4 (5 mmol,2.34 g) is dissolved in 50mL tetrahydrofuran, adipic anhydride (10 mmol,1.28 g) is weighed and added into the solution, the solution is heated in an oil bath, refluxed and stirred for reaction for 8 hours at 60 ℃, cooled to room temperature, 200mL of 10mol/L HCl aqueous solution and 200mL of toluene are added for extraction, the toluene layer is washed with hot water at 60 ℃ until the toluene layer is neutral, and 1.8g of compound NP is obtained after the solvent is rotationally evaporated from the toluene layer 4 -COOH， 1 HNMR(300MHz,CDCl 3 ):11.87(s,-COOH),8.68(d,1H)，8.22-8.28(m,2H)，7.74(d,1H)，7.57(t,1H)，7.26-7.39(m,10H)，7.08(d,2H)，7.04(s,1H)，6.58(d,1H)，6.39(d,1H)，2.72(q,2H)，2.35(t,2H)，2.21(t,2H)，1.50-1.66(m,4H)，1.18(t,3H)；HRMS(ESI,m/z):[M+H] + calcd for(C 40 H 34 O 5 ) 595.2479; found,595.2473, equation:
(2) Weighing 1.30g of hydroxyethyl cellulose (HEC) with molecular weight of 100000 and NP 4 Adding (1.49 g, 2.5 mmol) COOH and DMAP (3 mmol,0.37 g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of 0.8mmol/mL DCC tetrahydrofuran solution into the system under ice bath, stirring after the addition, reacting for 2h, then stirring at room temperature for further reaction for 24h, slowly pouring the reaction solution into 60 ℃ hot water while stirring after the reaction is completed, precipitating purple floccules, filtering, washing 3 times with 60 ℃ hot water, and vacuum drying to obtain 1.3g compound NP 4 -HEC；
(3) Weighing NP 4 HEC (1.2 g) was added to the flask, and 60g of pure water was added thereto, in the followingStirring for 6h at 70 ℃, stirring for 8h at room temperature, and centrifuging to obtain 61.2g of functional hydrogel.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 5
(1) 3,3' -Dimethoxyphenyl-3, 13-Dihydronaphthopyran [2,1-f]-13-ol NP 5 (5 mmol,2.50 g) is dissolved in 50mL tetrahydrofuran, succinic anhydride (10 mmol,1.00 g) is weighed and added into the solution, the mixture is heated, refluxed and stirred at 60 ℃ for reaction for 8 hours, cooled to room temperature, 200mL of 10mol/L HCl aqueous solution and 200mL of toluene are added for extraction, the toluene layer is washed with hot water at 60 ℃ until the toluene layer is neutral, and 2.1g of compound NP is obtained after the toluene layer is rotationally evaporated to obtain the solvent 5 -COOH， 1 HNMR(300MHz,CDCl 3 ):12.18(s,-COOH),8.68(d,1H)，8.22-8.28(m,2H)，7.74(d,1H)，7.57(t,1H)，7.26-7.39(m,7H)，7.04(s,1H)，6.89(d,4H)，6.58(d,1H)，6.39(d,1H)，3.81(s,6H)，2.71(t,2H)，2.52(t,2H)；HRMS(ESI,m/z):[M+H] + calcd for(C 38 H 30 O 7 ) 599.2064; found,599.2053, equation:
(2) Weighing hydroxypropyl cellulose (HPC) 1.30g and NP with molecular weight of 100000 5 Adding (1.37 g) of DMAP (3 mmol,1.50 g) and (2.5 mmol) of COOH into 25mL of tetrahydrofuran for complete dissolution, then dropwise adding 5mL of 0.8mmol/mL of DCC tetrahydrofuran solution into the system under ice bath, stirring after the dropwise addition, reacting for 2 hours, stirring at room temperature again for continuous stirring for 24 hours, slowly pouring the reaction solution into hot water at 60 ℃ with stirring after the reaction is finished, precipitating purple floccules, filtering, washing 3 times with hot water at 60 ℃, and vacuum drying to obtain 1.3g of compound NP 5 -HPC；
(3) Weighing NP 5 HPC (1.2 g) was added to the flask, and 60g of pure water was added thereto, and stirred at 70℃for 6 hours, at room temperature for 8 hours, and centrifuged to obtain 61.2g of a functional hydrogel.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 6
(1) 6, 11-dimethyl-3, 3' -dimethoxyphenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 6 (5 mmol,2.64 g) is dissolved in 50mL tetrahydrofuran, tetrahydrophthalic anhydride (10 mmol,1.52 g) is weighed and added into the solution, the solution is heated in an oil bath, refluxed and stirred for reaction for 8 hours at 60 ℃, cooled to room temperature, 200mL of 10mol/L HCl aqueous solution and 200mL of toluene are added for extraction, the toluene layer is washed with hot water at 60 ℃ until the toluene layer is neutral, and 2.2g of compound NP is obtained after the toluene layer is rotationally evaporated to obtain the solvent 6 -COOH， 1 H NMR(300MHz,CDCl 3 ):12.13(s,-COOH),8.17-8.23(m,2H)，7.65(d,1H)，7.62(s,1H)，7.45(d,1H)，7.28(d,4H)，7.04(s,1H)，6.89(d,4H)，6.84(d,1H)，6.58(d,1H)，6.39(d,1H)，5.65(m,2H)，3.81(s,6H)，3.15(q,1H)，2.80(q,1H)，2.66(s,3H)，2.04-2.45(m,7H)；HRMS(ESI,m/z):[M+H] + calcd for(C 44 H 38 O 7 ) 679.2690; found,679.2684, equation:
(2) Weighing hydroxypropyl cellulose (HPC) 1.30g and NP with molecular weight of 100000 6 -COOH(2.5mmol，1.70g)、DMAP (3 mmol,0.37 g) is added into 25mL tetrahydrofuran for full dissolution, then 5mL of DCC tetrahydrofuran solution with the concentration of 0.8mmol/mL is dripped into the system under ice bath, the reaction is stirred for 2h after the dripping is finished, the reaction is continued to be stirred at room temperature for 24h, after the reaction is finished, the reaction solution is slowly poured into hot water with the temperature of 60 ℃ while being stirred, purple floccules are separated out, filtered, and washed 3 times with hot water with the temperature of 60 ℃, and 1.2g of compound NP is obtained after vacuum drying 6 -HPC；
(3) Weighing NP 6 HPC (1.2 g) was added to the flask, and 60g of pure water was added thereto, and stirred at 70℃for 6 hours, at room temperature for 8 hours, and centrifuged to obtain 61.2g of a functional hydrogel.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 7
(1) 11-ethyl-3-methoxyphenyl-3' -ethylphenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 7 (5 mmol,1.96 g) was dissolved in 50mL tetrahydrofuran, phthalic anhydride (10 mmol,1.48 g) was weighed and added to the solution, the mixture was heated in an oil bath at 60℃under reflux and stirred for reaction for 8 hours, cooled to room temperature, extracted with 200mL of aqueous HCl solution of 10mol/L and 200mL of toluene, the toluene layer was washed with hot water at 60℃until it became neutral, and 1.7g of compound NP was obtained by rotary evaporation of the solvent from the toluene layer 7 -COOH， 1 H NMR(300MHz,CDCl 3 ):13.29(s,-COOH),8.68(d,1H)，8.12-8.29(m,4H)，7.81-7.86(m,2H)，7.66(s,1H)，7.49(d,1H)，7.26-7.32(m,6H)，7.08(d,2H)，7.04(s,1H)，6.89(d,2H)，6.58(d,1H)，6.39(d,1H)，3.81(s,3H)，2.72(q,4H)，1.18(t,6H)；HRMS(ESI,m/z):[M+H] + calcd for(C 45 H 36 O 6 ),539.1853; found,539.1861, equation:
(2) Weighing 1.30g of hydroxyethyl methylcellulose (HEMC) with molecular weight of 100000 and NP 7 Adding (1.35 g, 2.5 mmol) COOH and DMAP into 25mL tetrahydrofuran for fully dissolving, then dropwise adding 5mL of 0.8mmol/mL DCC tetrahydrofuran solution into the system under ice bath, stirring for 2h after the dropwise adding, stirring at room temperature again for continuous stirring for 24h, slowly pouring the reaction solution into hot water at 60 ℃ with stirring after the reaction is completed, precipitating purple floccules, filtering, washing with hot water at 60 ℃ for 3 times, and vacuum drying to obtain 1.3g compound NP 7 -HEMC；
(3) Weighing NP 7 HEMC (1.2 g) was added to the flask, 60g of pure water was added thereto, stirred at 70℃for 6 hours, and stirred at room temperature for 8 hours again, and after centrifugation, 61.2g of a functional hydrogel was obtained.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 8
(1) 11-isopropyl-3-ethoxyphenyl-3' -phenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 8 (5 mmol,2.63 g) was dissolved in 50mL tetrahydrofuran, then 2, 3-pyridine dicarboxylic anhydride (10 mmol,1.49 g) was weighed and added to the solution, the mixture was heated in an oil bath at 60℃under reflux and stirred for 8 hours, cooled to room temperature, extracted with 200mL of aqueous HCl solution of 10mol/L and 200mL of toluene, the toluene layer was washed with hot water at 60℃until it became neutral, and the toluene layer was taken to be spun to evaporate the solventAfter that, 2.1g of compound NP was obtained 8 -COOH， 1 H NMR(300MHz,CDCl 3 ):12.75(s,-COOH),9.09(d,1H)，8.68(d,1H)，8.46(d,1H)，8.23-8.28(m,2H)，7.94(t,1H)，7.78(s,1H)，7.61(d,1H)，7.26-7.35(m,9H)，7.04(s,1H)，6.89(d,2H)，6.58(d,1H)，6.39(d,1H)，4.05(q,2H)，2.85-2.89(m,1H)，1.34(t,3H)，1.20(d,6H)；HRMS(ESI,m/z):[M+H] + calcd for(C 44 H 35 NO 6 ) 674.2537; found,674.2525, equation:
(2) Weighing 1.30g of hydroxyethyl methylcellulose (HEMC) with molecular weight of 100000 and NP 8 Adding (1.69 g, 2.5 mmol) COOH and DMAP (3 mmol,0.37 g) into 25mL tetrahydrofuran for complete dissolution, then dropwise adding 5mL of 0.8mmol/mL DCC tetrahydrofuran solution into the system under ice bath, stirring after the addition, reacting for 2h, then stirring at room temperature for further reaction for 24h, slowly pouring the reaction solution into 60 ℃ hot water while stirring after the reaction is completed, precipitating purple floccules, filtering, washing 3 times with 60 ℃ hot water, and vacuum drying to obtain 1.3g compound NP 8 -HEMC；
(3) Weighing NP 8 HEMC (1.2 g) was added to the flask, 60g of pure water was added thereto, stirred at 70℃for 6 hours, and stirred at room temperature for 8 hours again, and after centrifugation, 61.2g of a functional hydrogel was obtained.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 9
(1) 6, 11-dimethyl-3-isopropoxyphenyl-3' -phenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 9 (5 mmol,2.63 g) was dissolved in 50mL tetrahydrofuran, pyridine-3, 4-dicarboxylic anhydride (10 mmol,1.49 g) was then weighed and added to the solution, the mixture was heated in an oil bath at 60℃under reflux with stirring for 8 hours, cooled to room temperature, extracted with 200mL of aqueous HCl solution at 10mol/L and 200mL of toluene, the toluene layer was washed with hot water at 60℃until it became neutral, and 2.1g of compound NP was obtained by rotary evaporation of the solvent from the toluene layer 9 -COOH， 1 H NMR(300MHz,CDCl 3 ):13.29(s,-COOH),9.52(s,1H)，8.62(d,1H)，8.10-8.22(m,3H)，7.61-7.66(m,2H)，7.45(d,1H)，7.26-7.34(m,7H)，7.04(s,1H)，6.83-6.70(m,3H)，6.58(d,1H)，6.39(d,1H)，4.67-4.71(m,1H)，2.66(s,3H)，2.31(s,3H)，1.29(d,6H)；HRMS(ESI,m/z):[M+H] + calcd for(C 44 H 35 NO 6 ) 674.2537; found,674.2545, equation:
(2) Weighing hydroxypropyl methylcellulose (HPMC) 1.30g and NP with molecular weight of 100000 9 Adding (1.69 g, 2.5 mmol) COOH and DMAP (3 mmol,0.37 g) into 25mL tetrahydrofuran for complete dissolution, then dropwise adding 5mL of 0.8mmol/mL DCC tetrahydrofuran solution into the system under ice bath, stirring after the addition, reacting for 2h, then stirring at room temperature for further reaction for 24h, slowly pouring the reaction solution into 60 ℃ hot water while stirring after the reaction is completed, precipitating purple floccules, filtering, washing 3 times with 60 ℃ hot water, and vacuum drying to obtain 1.3g compound NP 9 -HPMC；
(3) Weighing NP 9 HPMC (1.2 g) was added to the flask, 60g of pure water was added thereto, stirred at 70℃for 6 hours, and stirred at room temperature for 8 hours again, and after centrifugation 61.2g of functional hydrogel was obtained.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 10
(1) 6 methyl-11-methoxy-3-methoxyphenyl-3' -ethylphenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 10 (5 mmol,2.85 g) was dissolved in 50mL tetrahydrofuran, 1, 8-naphthalene dicarboxylic anhydride (10 mmol,1.98 g) was weighed and added to the solution, the mixture was heated in an oil bath at 60℃under reflux and stirred for 8 hours, cooled to room temperature, extracted with 200mL of aqueous HCl solution (10 mol/L) and 200mL of toluene, the toluene layer was washed with hot water at 60℃until it became neutral, and 2.2g of compound NP was obtained by rotary evaporation of the solvent from the toluene layer 10 -COOH， 1 H NMR(300MHz,CDCl 3 ):13.21(s,-COOH),8.65-8.72(m,2H)，8.50(d,2H)，8.21-8.25(m,2H)，7.86-7.79(m,2H)，7.65(d,1H)，7.36(s,1H)，7.28(d,4H)，7.19(d,1H)，7.08(d,2H)，7.04(s,1H)，6.83-6.90(m,3H)，6.58(d,1H)，6.39(d,1H)，4.67-4.70(m,1H)，3.70(s,3H)，2.72(q,2H)，2.66(s,3H)，1.29(d,6H)，1.18(t,3H)；HRMS(ESI,m/z):[M+H] + calcd for(C 51 H 42 O 7 ) 767.3003; found,767.3025, equation:
(2) Weighing hydroxypropyl methylcellulose (HPMC) 1.30g and NP with molecular weight of 100000 10 Adding (1.92 g, 2.5 mmol) COOH and DMAP (3 mmol,0.37 g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of 0.8mmol/mL DCC tetrahydrofuran solution into the system under ice bath, stirring after the addition, reacting for 2h, then stirring at room temperature for further reaction for 24h, slowly pouring the reaction solution into 60 ℃ hot water while stirring after the reaction is completed, precipitating purple floccules, filtering, washing 3 times with 60 ℃ hot water, and vacuum drying to obtain 1.2g compound NP 10 -HPMC；
(3) Weighing NP 10 HPMC (1.2 g) was added to the flask, 60g of pure water was added thereto, stirred at 70℃for 6 hours, and stirred at room temperature for 8 hours again, and after centrifugation 61.2g of functional hydrogel was obtained.
(4) The four sides of the glass are well adhered by using adhesive tapes, a cavity with the thickness of 2mm is formed between the two pieces of glass, a gap is reserved, 10g of functional hydrogel is filled between the two pieces of glass from the gap, and then a small amount of adhesive tapes are used for sealing the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Comparative example 1
1.2g of HEC with the molecular weight of 100000 is weighed and added into a flask, 60g of pure water is added into the flask, the mixture is stirred for 6 hours at 70 ℃, the temperature is changed to room temperature, the mixture is stirred for 8 hours, the thermal hydrogel is obtained after centrifugation, and finally 10g of thermal hydrogel is filled and injected between double-layer glass, and the single-thermal-regulation intelligent glass is obtained after sealing. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Comparative example 2
Weighing 1.2g of HPC with the molecular weight of 100000, adding 60g of pure water into the flask, stirring for 6 hours at 70 ℃, stirring for 8 hours at room temperature, centrifuging to obtain thermal hydrogel, filling 10g of thermal hydrogel into the space between the double-layer glass, and sealing to obtain the single thermal-regulating intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Comparative example 3
Weighing HPMC with molecular weight of 100000 and 1.2g, adding 60g of pure water into the flask, stirring at 70deg.C for 8h, centrifuging to obtain thermal hydrogel, filling 10g of thermal hydrogel into the space between double glass layers, and sealing to obtain single thermal-regulating intelligent glass. The visible light transmittance and infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Table 1: visible light transmittance of intelligent glass under different weather conditions
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Note that: the data are averages of multiple measurements at different times.
Table 2: infrared blocking rate of intelligent glass under different weather conditions
Note that: the data are averages of multiple measurements at different times.
As can be seen from tables 1 and 2, the photo-thermal double-regulation intelligent glass has good self-regulation capability for various weather, and the temperature is not too high in the daytime of the shade and can not reach the thermal critical temperature, so that the glass is not two-fold with the common glass, and has high visible light transmittance and low infrared blocking rate; when the temperature is not too high in sunny days, ultraviolet rays are emitted by the sun at the moment, so that the glass is changed from colorless transparent to colored transparent, the higher the temperature is, the stronger the sunlight is, the darker the glass is, the lower the visible light transmittance is, the more 80% is reduced to about 30%, the change is obvious, the infrared blocking rate is also enhanced along with the temperature rise, namely the heat insulation capacity is gradually enhanced along with the temperature rise; when the temperature is higher than 38 ℃, the glass temperature can reach the thermal change critical temperature due to self heat absorption, the glass is changed from dark transparent to dark opaque, the visible light transmittance is lowered, but the infrared blocking rate is increased to be the highest, namely the heat insulation efficiency is the strongest, the heat insulation effect is obvious, the indoor temperature is not overhigh, and the method is very in line with the expectations of people on intelligent glass. The single heat-regulating intelligent glass has no such good performance, and has very low infrared blocking rate, namely poor heat insulation effect, although the single heat-regulating intelligent glass has very good visible light transmittance in sunny days and under the condition that the air temperature is not too high, which is undesirable; and the infrared blocking rate is not as high as that of the photo-thermal double-regulation intelligent glass under the same condition when the air temperature is too high, namely the heat insulation effect is not as good as that of the photo-thermal double-regulation intelligent glass. It is worth mentioning that the heat insulation effect of the photo-thermal double-regulation intelligent glass is excellent at about 35 ℃, while the single-thermal-regulation intelligent glass can achieve similar effect at >38 ℃, and the photo-thermal double-regulation intelligent glass is obviously more excellent at the same temperature of >38 ℃. In a comprehensive view, the photo-thermal double-regulation intelligent glass has more excellent performance and can meet the requirements of people on the intelligent glass.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (10)
1. The preparation method of the photo-thermal double-regulation intelligent glass is characterized by comprising the following steps of:
firstly, adding naphthopyran compound NP into tetrahydrofuran for dissolution, adding anhydride, heating, refluxing and stirring for full reaction to obtain compound NP-COOH;
the molar ratio of the naphthopyran compound NP to the anhydride is 1 (0.5-5);
the structure of the naphthopyran compound NP is shown as follows:
wherein R is 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, C1-C10 alkyl, C1-C10 alkoxy;
the anhydride is at least one of succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride, 1-cyclopentene-1, 2-dicarboxylic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, 2, 3-pyridine dicarboxylic anhydride, pyridine-3, 4-dicarboxylic anhydride, isatoic anhydride, 1, 8-naphthalene dicarboxylic anhydride and 2, 3-naphthalene dicarboxylic anhydride;
adding cellulose and the compound NP-COOH and DMAP prepared in the first step into tetrahydrofuran for full dissolution, then dropwise adding a tetrahydrofuran solution of DCC into the system under ice bath, stirring for reaction after the dropwise adding is finished, and then stirring for reaction at room temperature to obtain the compound NP-cellulose;
the cellulose is at least one selected from methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose and hydroxyethyl methylcellulose;
thirdly, heating, stirring and mixing the compound NP-cellulose prepared in the second step with pure water, then stirring and reacting at room temperature, and centrifuging to obtain the functional hydrogel; the mass ratio of the NP-cellulose prepared in the second step to the pure water is 1 (30-65);
fourthly, sticking the adhesive tape on four sides of the glass to form a cavity between the two pieces of glass, reserving a gap, filling the functional hydrogel between the two pieces of glass from the gap, and then taking the adhesive tape to seal the gap to obtain the photo-thermal double-regulation intelligent glass.
2. The method for preparing photo-thermal double-regulation intelligent glass according to claim 1, wherein in the first step, naphthopyran compounds NP and R 1 、R 2 、R 3 、R 4 Each independently selected from hydrogen, -CH 3 、-C 2 H 5 、-CH 2 CH 2 CH 3 、-CH(CH 3 ) 2 、-CH 2 CH 2 CH 2 CH 3 、-OCH 3 、-OC 2 H 5 、-OCH 2 CH 2 CH 3 、-OCH(CH 3 ) 2 、-O CH 2 CH 2 CH 2 CH 3 。
3. The method for preparing photo-thermal dual-regulation intelligent glass according to claim 2, wherein in the first step, the structure of the naphthopyran compound NP is selected from one of the following structures:
4. the method for preparing photo-thermal double-regulation intelligent glass according to claim 1, wherein in the second step, the mass ratio of the compound NP-COOH prepared in the first step to cellulose is 1 (0.1-2);
in the second step, the molar ratio of the compound NP-COOH to DMAP prepared in the first step is 1 (0.8-2).
5. The method for preparing photo-thermal double-regulation intelligent glass according to claim 1, wherein in the second step, the molar ratio of the compound NP-COOH to DCC prepared in the first step is 1 (0.5-3);
in the second step, the molar quantity of the compound NP-COOH prepared in the first step and the volume ratio of tetrahydrofuran are 1mmol (5-20 mL).
6. The method for preparing photo-thermal double-regulation intelligent glass according to claim 1, wherein in the second step, the concentration of tetrahydrofuran solution of DCC is 0.5-1.2mmol/mL;
and in the second step, stirring and reacting for 1-3 hours after the dripping is finished.
7. The method for preparing photo-thermal double-regulation intelligent glass according to claim 1, wherein the second step is carried out at room temperature for continuous stirring reaction for 1-24 h;
the temperature of heating, stirring and mixing in the third step is 60-80 ℃ and the time is 5-10 h.
8. The method for preparing photo-thermal double-regulation intelligent glass according to claim 1, wherein the stirring reaction time at room temperature in the third step is 5-10 h;
and in the fourth step, the distance between the two pieces of glass is 0.18-0.23 mm.
9. The method for preparing photo-thermal double-regulation intelligent glass according to claim 1, wherein the fourth step is characterized in that the amount of the functional hydrogel filled between two pieces of glass is as follows: every 1m 2 0.8-1.2 kg of glass injection functional hydrogel.
10. The method for preparing photo-thermal double-regulation intelligent glass according to claim 1, wherein the dimensions of the glass are as follows: float glass having a length and width of 10cm×10cm and a thickness of 3mm.
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