CN114934737A - Preparation method of photo-thermal double-regulation intelligent glass - Google Patents
Preparation method of photo-thermal double-regulation intelligent glass Download PDFInfo
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- CN114934737A CN114934737A CN202210506455.5A CN202210506455A CN114934737A CN 114934737 A CN114934737 A CN 114934737A CN 202210506455 A CN202210506455 A CN 202210506455A CN 114934737 A CN114934737 A CN 114934737A
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- 239000011521 glass Substances 0.000 title claims abstract description 129
- 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 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 44
- 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 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
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920002678 cellulose Polymers 0.000 claims abstract description 16
- 239000001913 cellulose Substances 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 13
- -1 naphthopyran compound Chemical class 0.000 claims abstract description 12
- 238000004090 dissolution Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 7
- 238000011049 filling Methods 0.000 claims abstract description 7
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims abstract 3
- 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
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 9
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 7
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 7
- 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
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 4
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 4
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 4
- 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 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
- 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
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-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
- 230000035484 reaction time Effects 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
- 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
- 239000004984 smart glass Substances 0.000 claims 8
- 238000007789 sealing Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 93
- 230000000903 blocking effect Effects 0.000 description 29
- 238000002834 transmittance Methods 0.000 description 26
- 238000005303 weighing Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- 238000005406 washing Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000009413 insulation Methods 0.000 description 10
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000008213 purified water Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000544583 Heterococcus <yellow-green algae> Species 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009118 appropriate response Effects 0.000 description 1
- 230000004888 barrier function 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
- 238000013461 design Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
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- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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: dissolving a naphthopyran compound NP in tetrahydrofuran, adding acid anhydride, heating, refluxing and stirring for full reaction to obtain a compound NP-COOH; adding cellulose, compound NP-COOH and DMAP into tetrahydrofuran for full dissolution, then dropwise adding a tetrahydrofuran solution of DCC into the system under ice bath, stirring for reaction after dropwise adding, and then continuously stirring for reaction at room temperature to obtain a compound NP-cellulose; heating, stirring and mixing a compound NP-cellulose and pure water, then stirring and reacting at room temperature, and centrifuging to obtain functional hydrogel; and (3) adhering adhesive tapes on four sides of the glass to form a cavity between the two pieces of glass, leaving a gap, filling the functional hydrogel between the two pieces of glass from the gap, and sealing the gap by using the adhesive tapes to obtain the photo-thermal double-regulation 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 a material with intelligent characteristics of sensing environmental (including internal environment and external environment) stimulation, analyzing, processing and judging the environmental stimulation, and taking certain measures to perform appropriate response. The intelligent material is a fourth generation material following natural materials, synthetic polymer materials and artificial design materials, is one of important development directions of modern high and new materials, supports the development of future high and new technologies, gradually eliminates the boundary between functional materials and structural materials in the traditional sense, and realizes structural functionalization and functional diversification.
In the building industry, building material intellectualization also gradually deepens into people's mind. Among them, the energy consumption of the building caused by the glass windows and doors is considerable, and especially when sunlight is involved, the problems of transmittance and absorptivity are more noticeable to many researchers. At present, the intelligent glass mainly takes photochromic glass as main material, and the photochromic glass which is researched mainly comprises thermochromic glass, electrochromic glass, photochromic glass and gasochromic glass.
Regarding a single thermochromic glass, the general thermochromic glass has a high discoloration critical temperature, and can discolor and insulate heat in particularly hot weather because a hydrogel-type thermochromic material becomes opaque after discoloration, so that the light transmittance is affected, and if the discoloration temperature is set to be low, the appearance of a user is often affected. This results in the thermochromic glass being used in hot weather without much effort; for electrochromic glass, the electrochromic glass needs to be electrified to achieve the effect of color change and heat insulation, which per se violates the original purpose of green energy conservation; in the case of a single photochromic glass, the glass performs well in hot weather, but the heat insulation effect reaches the limit in the case of particularly hot weather, thereby causing poor heat insulation effect; although the system structure of the color-changing device in the gasochromic glass is simple, the preparation cost is relatively high in practical application, and the large-scale production is not easy.
In a word, the limitation of a single adjusting method is large, and the manufactured intelligent glass has 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 purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of photo-thermal dual-regulation intelligent glass, which comprises the following steps:
firstly, adding a naphthopyran compound NP into tetrahydrofuran for dissolving, adding acid anhydride, heating, refluxing and stirring for full reaction to obtain a compound NP-COOH;
the mol ratio of the naphthopyran compound NP to the acid 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 acid anhydride is selected from at least one of succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride, 1-cyclopentene-1, 2-dicarboxylic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, 2, 3-pyridinedicarboxylic anhydride, pyridine-3, 4-dicarboxylic anhydride, isatoic anhydride, 1, 8-naphthalic anhydride and 2, 3-naphthalic anhydride;
secondly, adding the cellulose and the compounds 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 dropwise adding, and then continuously stirring for reaction at room temperature to obtain a compound NP-cellulose;
the cellulose is at least one selected from methylcellulose, 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 functional hydrogel; the mass ratio of the NP-cellulose prepared in the second step to the pure water is 1 (30-65);
and fourthly, adhering adhesive tapes on four sides of the glass to form a cavity between the two pieces of glass, leaving a gap, filling the functional hydrogel between the two pieces of glass from the gap, and then taking the adhesive tapes to seal the gap to obtain the photo-thermal double-regulation intelligent glass.
The molar weight of the naphthopyran compound NP and the volume ratio of the tetrahydrofuran in the first step are 1mmol (5-20 mL).
Preferably, in said first step, the naphthopyran compound 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 the 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 for heating, refluxing and stirring to fully react 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 the cellulose is 1 (0.1-2).
In the second step, the molar ratio of the compound NP-COOH prepared in the first step to DMAP is 1 (0.8-2), preferably 1: 1.2.
In the second step, the molar ratio of the compound NP-COOH prepared in the first step to DCC is 1 (0.5-3).
In the second step, the ratio of the molar weight of the compound NP-COOH prepared in the first step to the volume of tetrahydrofuran is 1mmol (5-20 mL).
In the second step, the concentration of the tetrahydrofuran solution of DCC is 0.5-1.2 mmol/mL.
And in the second step, the stirring reaction time is 1-3 h after the dropwise addition is finished.
And in the second step, the room temperature is transferred and the reaction is continuously stirred for 1-24 hours.
And the heating, stirring and mixing in the third step are carried out at the temperature of 60-80 ℃ for 5-10 hours.
And in the third step, the stirring reaction time at room temperature is 5-10 h.
And in the fourth step, the distance between the two pieces of glass is 0.18-0.23 mm, and preferably 0.20 mm.
And in the fourth step, the dosage of the functional hydrogel filled between the two pieces of glass is as follows: every 1m 2 0.8-1.2 kg of glass-impregnated functional hydrogel, preferably 1.0 kg.
The size of the glass: float glass having a length and width of 10cm × 10cm and a thickness of 3 mm.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
compared with the single-regulation intelligent glass, the glass prepared by the method can be flexibly self-regulated according to the change of weather, and when the weather is cold, the infrared blocking rate is about 12%, and the solar heat can hardly be blocked from entering a room; when the weather is hot, the infrared blocking rate can reach more than 80 percent, so that most heat can be blocked from entering a room, and the indoor environment is really warm in winter and cool in summer; due to the characteristics of the photochromic material, the photochromic material can absorb ultraviolet rays to achieve the color changing effect, thereby effectively blocking the ultraviolet rays and reducing the damage of the ultraviolet rays to human bodies; the process is simple, the cost is low, and the industrial production is easy to realize; pure water is used as a solvent, so that excessive organic reagents are not used in the whole process, and the environment is protected; the indoor temperature can be effectively adjusted, the use of electrical appliances such as an air conditioner and the like is reduced, and the purpose of solving the energy-saving problem from the source is achieved.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The principle of the photo-thermal double-regulation intelligent glass provided by the invention is as follows: the thermal response functional hydrogel prepared from the cellulose has special properties, is colorless and transparent when the temperature is less than 50 ℃, and is white and opaque when the temperature is more than 50 ℃, so that the effect of blocking infrared radiation and thermal radiation by glass is effectively achieved, and the effect of blocking 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 weak sunlight, and can be colored and transparent under the condition of sunlight irradiation, so that the effects of effectively blocking high-energy ultraviolet rays and partially blocking heat are achieved, and the blocking effect can be optimal in the noon or in the summer. Generally, the phase transition temperature of the thermal response hydrogel is higher, and the hydrogel is opaque after phase transition and has great entrance and exit with an actual application scene; the technical scheme of the photochromic composition mainly isolates ultraviolet rays and has no high-efficiency barrier effect on most of 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 rejection rate at a low temperature, higher visible light transmittance and higher infrared rejection rate at a high temperature, and when the temperature is higher and reaches the hydrogel color change temperature, the glass has low visible light transmittance and higher infrared rejection rate.
The intelligent glass is characterized in that: under the condition of cloudy days, the temperature is not too high generally, and at the moment, the glass does not influence the transmission of light and the transmission of heat and is represented as common glass. Under the sunny condition, when the temperature is below 30 ℃, the glass is light and transparent, and basically cannot block heat from entering a cold room; when the temperature is 30-38 ℃, the glass is dark and 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 double-response method to intelligently adjust the ultraviolet blocking rate and the infrared thermal radiation blocking rate of the glass, so as to achieve the effect of being warm in winter and cool in summer indoors, and reduce carbon emission and energy consumption.
The glass used in the examples of the present invention was float glass (hereinafter referred to as glass) having a length and width of 10cm × 10cm and a thickness of 3mm, which was obtained from Shanghai Yuntian glass Co., Ltd; the adhesive tape used was purchased from Shenzhen, Baoan Songtangxing adhesive products, 2mm wet-process 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 (5mmol, 2.20g) (the Synthesis method refers to Qian Zhuao, Yanhua Yang, Yinxiang Duan, Xiao Tao, Yingzhong Shen. Synthesis and Photonic Properties of naphthalene symmetry polyester Substituents. chem. Heterococcus. Com.2018.) are dissolved in 50mL tetrahydrofuran, succinic anhydride (10mmol, 1.00g) is added into the solution, the mixture is heated and refluxed and stirred for reaction at the temperature of 60 ℃ for 8h, the mixture is cooled to room temperature, 10mol/L of HCl aqueous solution 200mL and 200mL of toluene are added for extraction, the toluene layer is washed to be neutral by 60 ℃ of hot water, and 1.8g of the compound NP is obtained after the toluene layer is taken out and the solvent is evaporated in a rotating way 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, the reaction formula is as follows:
(2) mixing hydroxymethyl cellulose (HMC)1.30g with molecular weight of 100000, NP 1 adding-COOH (2.5mmol, 1.35g) and DMAP (3mmol, 0.37g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of DCC tetrahydrofuran solution with the concentration of 0.8mmol/mL into the system under ice bath, stirring for reaction for 2h after dropwise adding, then continuing stirring at room temperature for reaction for 24h, after the reaction is finished, slowly pouring the reaction liquid into 60 ℃ hot water while stirring, separating out purple floccules, filtering, washing 3 times with 60 ℃ hot water, and drying in vacuum to obtain 1.23g of compound NP 1 -HMC；
(3) 1.2g NP 1 HMC was added to the flask, 60g of purified water was added thereto, stirred at 70 ℃ for 6 hours, stirred at room temperature for 8 hours, and centrifuged to obtain 61.2g of functional hydrogel.
(4) Adhesive tapes are adhered to four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the 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: and (3) after the photo-thermal double-regulation intelligent glass is placed for 10 minutes, detecting by using an on-forest LS183 transmittance detector, recording data, repeating the operation for multiple times on different dates, and filling the average value into table 1.
Example 2
(1) Reacting 3-methylphenyl-3' -phenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 2 (5mmol, 2.27g) was dissolved in 50mL of tetrahydrofuran and maleic anhydride (10 m)mol, 0.98g) is added into the solution, oil bath heating reflux stirring reaction is carried out for 8 hours at the temperature of 60 ℃, the solution is cooled to room temperature, 200mL of HCl aqueous solution and 200mL of toluene with the concentration of 10mol/L are added for extraction, the toluene layer is washed by hot water with the temperature of 60 ℃ until the toluene layer is neutral, and 1.9g of compound NP is obtained after the toluene layer is taken to evaporate the solvent by rotation 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, the reaction formula is as follows:
(2) mixing hydroxymethyl cellulose (HMC)1.30g with molecular weight of 100000, NP 2 adding-COOH (2.5mmol, 1.38g) and DMAP (3mmol, 0.37g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of DCC tetrahydrofuran solution with the concentration of 0.8mmol/mL into the system under ice bath, stirring for reaction for 2h after dropwise adding, then continuing stirring at room temperature for reaction for 24h, after the reaction is finished, slowly pouring the reaction liquid into 60 ℃ hot water while stirring, separating out purple floccules, filtering, washing 3 times with 60 ℃ hot water, and drying in vacuum to obtain 1.25g of compound NP 2 -HMC；
(3) Weighing NPs 2 HMC (1.2g) was added to the flask, 60g of pure water was added thereto, and the mixture was stirred at 70 ℃ for 6 hours, then at room temperature for 8 hours, and then centrifuged to obtain 61.2g of a functional hydrogel.
(4) Adhesive tapes are adhered to the four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the 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 (5mmol, 2.34g) is dissolved in 50mL tetrahydrofuran, glutaric anhydride (10mmol, 1.14g) is weighed and added into the solution, the mixture is heated in oil bath at 60 ℃ and stirred under reflux for 8h, the mixture is cooled to room temperature, 10mol/L HCl aqueous solution 200mL and 200mL toluene are added for extraction, the toluene layer is washed by 60 ℃ hot water until the toluene layer is neutral, and the solvent is evaporated by rotation of the toluene layer, so that 1.9g of compound NP is obtained 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, the reaction formula is as follows:
(2) weighing hydroxyethyl cellulose (HEC) with molecular weight of 100000 1.30g, NP 3 adding-COOH (2.5mmol, 1.45g) and DMAP (3mmol, 0.37g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of DCC tetrahydrofuran solution with the concentration of 0.8mmol/mL into the system under ice bath, stirring for reaction for 2h after dropwise adding, then continuing stirring at room temperature for reaction for 24h, after the reaction is finished, slowly pouring the reaction liquid into 60 ℃ hot water while stirring, separating out purple floccules, filtering, washing 3 times with 60 ℃ hot water, and drying in vacuum to obtain 1.3g of compound NP 3 -HEC；
(3) Weighing NPs 3 -HEC (1.2g) was added to the flask, 60g of purified water was added thereto, and the mixture was stirred at 70 ℃ for 6 hours, then at room temperature for 8 hours, and centrifuged to obtain61.2g of functional hydrogel.
(4) Adhesive tapes are adhered to the four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 4
(1) Reacting 3-ethylphenyl-3' -phenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 4 Dissolving (5mmol, 2.34g) in 50mL tetrahydrofuran, weighing adipic anhydride (10mmol, 1.28g) and adding into the solution, heating in oil bath at 60 deg.C under reflux and stirring for 8h, cooling to room temperature, adding 10mol/L HCl aqueous solution 200mL and 200mL toluene for extraction, washing the toluene layer with 60 deg.C hot water to neutrality, taking the toluene layer, and rotary evaporating to remove solvent to obtain 1.8g NP 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, the reaction formula is as follows:
(2) weighing hydroxyethyl cellulose (HEC) with molecular weight of 100000 1.30g, NP 4 adding-COOH (2.5mmol, 1.49g) and DMAP (3mmol, 0.37g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of DCC tetrahydrofuran solution with the concentration of 0.8mmol/mL into the system under ice bath, stirring for reaction for 2h after dropwise adding, then continuing stirring at room temperature for reaction for 24h, after the reaction is finished, slowly pouring the reaction liquid into 60 ℃ hot water while stirring, separating out purple floccules, filtering, washing 3 times with 60 ℃ hot water, and drying in vacuum to obtain 1.3g of compound NP 4 -HEC；
(3) Weighing NPs 4 -HEC (1.2g) was added to the flask, 60g of pure water was added thereto, stirred at 70 ℃ for 6h, then at room temperature for 8h, and centrifuged to obtain 61.2g of functional hydrogel.
(4) Adhesive tapes are adhered to the four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the 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 Dissolving (5mmol, 2.50g) in 50mL tetrahydrofuran, weighing succinic anhydride (10mmol, 1.00g) and adding into the solution, heating in oil bath at 60 deg.C under reflux and stirring for 8h, cooling to room temperature, adding 10mol/L HCl aqueous solution 200mL and 200mL toluene for extraction, washing the toluene layer with 60 deg.C hot water to neutrality, taking the toluene layer, and rotary evaporating to remove solvent to obtain 2.1g NP 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, the reaction formula is as follows:
(2) weighing hydroxypropyl cellulose (HPC)1.30g with molecular weight of 100000, NP 5 -COOH (2.5mmol, 1.50g) and DMAP (3mmol, 0.37g) were added to 25mL of tetrahydrofuran to dissolve them sufficiently, and then 0 was added dropwise to the system while cooling on ice5mL of DCC tetrahydrofuran solution with concentration of 8mmol/mL, stirring for reaction for 2h after the dropwise addition, continuing stirring at room temperature for reaction for 24h, after the reaction is completed, slowly pouring the reaction solution into hot water with the temperature of 60 ℃ while stirring, separating out purple floccules, filtering, washing with hot water with the temperature of 60 ℃ for 3 times, and drying in vacuum to obtain 1.3g of compound NP 5 -HPC；
(3) Weighing NPs 5 HPC (1.2g) was added to the flask, 60g of pure water was further added thereto, and the mixture was stirred at 70 ℃ for 6 hours, then stirred at room temperature for 8 hours, and centrifuged to obtain 61.2g of a functional hydrogel.
(4) Adhesive tapes are adhered to four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 6
(1) Mixing 6, 11-dimethyl-3, 3' -dimethoxyphenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 6 Dissolving (5mmol, 2.64g) in 50mL tetrahydrofuran, weighing tetrahydrophthalic anhydride (10mmol, 1.52g) and adding into the solution, heating in oil bath at 60 deg.C under reflux and stirring for reaction for 8h, cooling to room temperature, adding 10mol/L HCl aqueous solution 200mL and 200mL toluene for extraction, washing toluene layer with 60 deg.C hot water to neutrality, taking toluene layer, and rotary evaporating solvent to obtain 2.2g NP compound 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, the reaction formula is as follows:
(2) weighing hydroxypropyl cellulose (HPC)1.30g with molecular weight of 100000, NP 6 adding-COOH (2.5mmol, 1.70g) and DMAP (3mmol, 0.37g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of DCC tetrahydrofuran solution with the concentration of 0.8mmol/mL into the system under ice bath, stirring for reaction for 2h after dropwise adding, then continuing stirring at room temperature for reaction for 24h, after the reaction is finished, slowly pouring the reaction liquid into 60 ℃ hot water while stirring, separating out purple floccules, filtering, washing 3 times with 60 ℃ hot water, and drying in vacuum to obtain 1.2g of compound NP 6 -HPC；
(3) Weighing NPs 6 HPC (1.2g) was added to the flask, 60g of pure water was further added thereto, and the mixture was stirred at 70 ℃ for 6 hours, then stirred at room temperature for 8 hours, and centrifuged to obtain 61.2g of a functional hydrogel.
(4) Adhesive tapes are adhered to the four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 7
(1) Reacting 11-ethyl-3-methoxyphenyl-3' -ethylphenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 7 Dissolving (5mmol, 1.96g) in 50mL tetrahydrofuran, weighing phthalic anhydride (10mmol, 1.48g) and adding into the solution, heating in oil bath at 60 deg.C under reflux and stirring for 8h, cooling to room temperature, adding 10mol/L HCl aqueous solution 200mL and 200mL toluene for extraction, washing the toluene layer with hot water at 60 deg.C until it is neutral, taking the toluene layer, and rotary evaporating to remove solvent to obtain 1.7g NP 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, the reaction formula is as follows:
(2) 1.30g of hydroxyethyl methylcellulose (HEMC) with molecular weight of 100000 and NP were weighed 7 adding-COOH (2.5mmol, 1.35g) and DMAP (3mmol, 0.37g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of DCC tetrahydrofuran solution with the concentration of 0.8mmol/mL into the system under ice bath, stirring for reaction for 2h after dropwise adding, then continuing stirring at room temperature for reaction for 24h, after the reaction is finished, slowly pouring the reaction liquid into 60 ℃ hot water while stirring, separating out purple floccules, filtering, washing 3 times with 60 ℃ hot water, and drying in vacuum to obtain 1.3g of compound NP 7 -HEMC；
(3) Weighing NPs 7 -HEMC (1.2g) was added to a flask, 60g of purified 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) Adhesive tapes are adhered to the four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 8
(1) Reacting 11-isopropyl-3-ethoxyphenyl-3' -phenyl-3, 13-dihydronaphthopyran [2,1-f ]]-13-ol NP 8 (5mmol, 2.63g) was dissolved inAdding 2, 3-pyridine dicarboxylic anhydride (10mmol, 1.49g) into 50mL tetrahydrofuran, heating in oil bath at 60 deg.C under reflux, stirring for reaction for 8h, cooling to room temperature, adding 10mol/L HCl aqueous solution 200mL and 200mL toluene, extracting, washing toluene layer with 60 deg.C hot water to neutrality, and rotary evaporating solvent to obtain 2.1g NP 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, the equation is as follows:
(2) weighing hydroxyethyl methylcellulose (HEMC)1.30g and NP with molecular weight of 100000 8 adding-COOH (2.5mmol, 1.69g) and DMAP (3mmol, 0.37g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of DCC tetrahydrofuran solution with the concentration of 0.8mmol/mL into the system under ice bath, stirring for reaction for 2h after dropwise adding, then continuing stirring at room temperature for reaction for 24h, after the reaction is finished, slowly pouring the reaction liquid into 60 ℃ hot water while stirring, separating out purple floccules, filtering, washing 3 times with 60 ℃ hot water, and drying in vacuum to obtain 1.3g of compound NP 8 -HEMC；
(3) Weighing NPs 8 -HEMC (1.2g) was added to a flask, 60g of purified 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) Adhesive tapes are adhered to the four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 9
(1) Reacting 6, 11-dimethyl-3-isopropoxyphenyl-3' -phenyl-3, 13-dihydronaphthopyran [2,1-f ]]-13-ol NP 9 Dissolving (5mmol, 2.63g) in 50mL tetrahydrofuran, weighing pyridine-3, 4-dicarboxylic anhydride (10mmol, 1.49g), adding into the solution, heating in oil bath at 60 deg.C under reflux, stirring for reaction for 8h, cooling to room temperature, adding 10mol/L HCl aqueous solution 200mL and 200mL toluene for extraction, washing the toluene layer with 60 deg.C hot water to neutrality, taking the toluene layer, and rotary evaporating to remove solvent to obtain 2.1g compound NP 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, the reaction formula is as follows:
(2) weighing hydroxypropyl methylcellulose (HPMC)1.30g and NP with molecular weight of 100000 9 adding-COOH (2.5mmol, 1.69g) and DMAP (3mmol, 0.37g) into 25mL tetrahydrofuran for full dissolution, then dropwise adding 5mL of DCC tetrahydrofuran solution with the concentration of 0.8mmol/mL into the system under ice bath, stirring for reaction for 2h after dropwise adding, then continuing stirring at room temperature for reaction for 24h, after the reaction is finished, slowly pouring the reaction liquid into 60 ℃ hot water while stirring, separating out purple floccules, filtering, washing 3 times with 60 ℃ hot water, and drying in vacuum to obtain 1.3g of compound NP 9 -HPMC；
(3) Weighing NPs 9 HPMC (1.2g) was added to the flask, 60g of purified water was added thereto, stirred at 70 ℃ for 6h, then at room temperature for 8h, and centrifuged to obtain 61.2g of functional hydrogel.
(4) Adhesive tapes are adhered to the four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Example 10
(1) Reacting 6 methyl-11-methoxy-3-methoxyphenyl-3' -ethylphenyl-3, 13-dihydronaphthopyran [2,1-f]-13-ol NP 10 Dissolving (5mmol, 2.85g) in 50mL tetrahydrofuran, weighing 1, 8-naphthalic anhydride (10mmol, 1.98g) and adding into the solution, heating in oil bath at 60 deg.C under reflux and stirring for reaction for 8h, cooling to room temperature, adding 10mol/L HCl aqueous solution 200mL and 200mL toluene for extraction, washing toluene layer with 60 deg.C hot water to neutrality, taking toluene layer, rotary evaporating solvent to obtain 2.2g NP compound 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, the reaction formula is as follows:
(2) weighing hydroxypropyl methylcellulose (HPMC)1.30g and NP with molecular weight of 100000 10 -COOH (2.5mmol, 1.92g), DMAP (3mmol, 0.37g) were added to 25mL of tetrahydrofuran to dissolve sufficiently, and then the mixture was poured into the system under ice bathDropwise adding 5mL of 0.8mmol/mL DCC tetrahydrofuran solution, stirring for reacting for 2h after dropwise adding, further stirring at room temperature for reacting for 24h, after the reaction is finished, slowly pouring the reaction solution into 60 ℃ hot water while stirring, separating out purple floccules, filtering, washing with 60 ℃ hot water for 3 times, and drying in vacuum to obtain 1.2g of compound NP 10 -HPMC；
(3) Weighing NPs 10 HPMC (1.2g) was added to the flask, 60g of purified water was added thereto, and the mixture was stirred at 70 ℃ for 6 hours, then at room temperature for 8 hours, and centrifuged to obtain 61.2g of a functional hydrogel.
(4) Adhesive tapes are adhered to the four sides of the glass, 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 plurality of adhesive tapes are taken to seal the gap to obtain the photo-thermal double-regulation intelligent glass. The visible light transmittance and the infrared blocking rate under different weather conditions were measured, and the results are shown in tables 1 and 2, respectively.
Comparative example 1
Weighing 1.2g of HEC with the molecular weight of 100000, adding into a flask, adding 60g of pure water, stirring at 70 ℃ for 6h, stirring at room temperature for 8h, centrifuging to obtain heat-altered hydrogel, filling 10g of the heat-altered hydrogel between double layers of glass, and sealing to obtain the single heat-adjusted intelligent glass. The visible light transmittance and the 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 into a flask, adding 60g of pure water, stirring at 70 ℃ for 6h, stirring at room temperature for 8h, centrifuging to obtain heat-altered hydrogel, filling 10g of the heat-altered hydrogel between double layers of glass, and sealing to obtain the single heat-adjusted intelligent glass. The visible light transmittance and the 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 the molecular weight of 100000 and 1.2g, adding into a flask, adding 60g of pure water, stirring at 70 ℃ for h, stirring at room temperature for 8h, centrifuging to obtain thermal-change hydrogel, filling 10g of thermal-change hydrogel between double-layer glass, and sealing to obtain the single thermal-regulation intelligent glass. The visible light transmittance and the 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
Note: the data are the average of multiple test results at different times.
Table 2: infrared blocking rate of intelligent glass under different weather conditions
Note: the data are the average of multiple test results at different times.
As can be seen from tables 1 and 2, the photo-thermal dual-regulation intelligent glass has good self-regulation capacity for various weathers, and in cloudy days, the temperature is not too high and cannot reach the thermal change critical temperature, so that the glass does not have the same effect as common glass in the cloudy days, and has high visible light transmittance and low infrared rejection rate; when the temperature is not too high in a sunny day, the glass is changed from colorless transparency to colored transparency due to the fact that the sun emits ultraviolet rays, the glass is changed from colorless transparency to colored transparency, the higher the temperature is, the stronger the sunlight is, the deeper the glass color is, the lower the visible light transmittance is, the more the visible light transmittance is reduced from more than 80% to about 30%, the change is obvious, the infrared blocking rate is also enhanced along with the temperature rise, the more the infrared blocking rate is increased from less than 15% to more than 65%, namely, the heat insulation capability is gradually enhanced along with the temperature rise; when the air 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 transparent deep color to opaque deep color, although the visible light transmittance can be lowered, the infrared blocking rate can be increased to the highest, about 85 percent, namely the heat insulation efficiency is the strongest, the heat insulation effect is obvious, the indoor air temperature can not be too high, and the intelligent glass is very suitable for the expectation of people on the intelligent glass. The single thermal regulation intelligent glass has no good performance, and has very good visible light transmittance in sunny days and under the condition that the air temperature is not too high, but the infrared blocking rate is very low, namely the thermal insulation effect is very poor, which is undesirable for people; and when the temperature is too high, the infrared blocking rate is not as high as that of the photo-thermal dual-regulation intelligent glass under the same condition, namely the heat insulation effect is not as good as that of the photo-thermal dual-regulation intelligent glass. It is worth mentioning that the heat insulation effect of the photo-thermal dual-regulation intelligent glass is excellent at about 35 ℃, the single-thermal-regulation intelligent glass can achieve similar effect only at the temperature of more than 38 ℃, and the photo-thermal dual-regulation intelligent glass is obviously more excellent under the condition that the temperature of the single-thermal-regulation intelligent glass is more than 38 ℃. In conclusion, the photo-thermal dual-regulation intelligent glass has more excellent performance and can better meet the requirements of people on the intelligent glass.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the photo-thermal double-regulation intelligent glass is characterized by comprising the following steps of:
firstly, adding a naphthopyran compound NP into tetrahydrofuran for dissolving, adding acid anhydride, heating, refluxing and stirring for full reaction to obtain a compound NP-COOH;
the mol ratio of the naphthopyran compound NP to the acid 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 acid anhydride is selected from at least one of succinic anhydride, maleic anhydride, glutaric anhydride, adipic anhydride, 1-cyclopentene-1, 2-dicarboxylic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, 2, 3-pyridinedicarboxylic anhydride, pyridine-3, 4-dicarboxylic anhydride, isatoic anhydride, 1, 8-naphthalic anhydride and 2, 3-naphthalic anhydride;
secondly, adding the cellulose and the compounds 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 dropwise adding, and then continuously stirring for reaction at room temperature to obtain a compound NP-cellulose;
the cellulose is at least one selected from methylcellulose, 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 functional hydrogel; the mass ratio of the NP-cellulose prepared in the second step to the pure water is 1 (30-65);
and fourthly, adhering adhesive tapes on four sides of the glass to form a cavity between the two pieces of glass, leaving a gap, filling the functional hydrogel between the two pieces of glass from the gap, and then taking the adhesive tapes to seal the gap to obtain the photo-thermal double-regulation intelligent glass.
2. The method for preparing photothermal double-regulating smart glass according to claim 1, wherein in the first step, the naphthopyran compound 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 。
3. The method for preparing photothermal double-regulating smart 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 photothermal double-regulating smart glass according to claim 1, wherein in the second step, the mass ratio of the compound NP-COOH prepared in the first step to the cellulose is 1 (0.1-2);
in the second step, the molar ratio of the compound NP-COOH prepared in the first step to DMAP is 1 (0.8-2).
5. The method for preparing photothermal double-tempered smart glass according to claim 1, wherein in the second step, the molar ratio of compound NP-COOH to DCC prepared in the first step is 1 (0.5-3);
in the second step, the ratio of the molar weight of the compound NP-COOH prepared in the first step to the volume of tetrahydrofuran is 1mmol (5-20 mL).
6. The method for preparing photothermal double-tempered smart glass according to claim 1, wherein in the second step, the concentration of the tetrahydrofuran solution of DCC is 0.5 to 1.2 mmol/mL;
and in the second step, the stirring reaction time is 1-3 h after the dropwise addition is finished.
7. The method for preparing the photothermal double-regulation smart glass according to claim 1, wherein the time for the second step of continuing stirring and reacting at room temperature is 1-24 hours;
and the heating, stirring and mixing in the third step are carried out at the temperature of 60-80 ℃ for 5-10 hours.
8. The method for preparing the photothermal double-regulation smart glass according to claim 1, wherein the stirring reaction at room temperature in the third step is carried out for 5-10 hours;
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 dual-regulation intelligent glass according to claim 1, wherein the dosage of the functional hydrogel filled between the two pieces of glass in the fourth step is as follows: every 1m 2 0.8-1.2 kg of glass-injected functional hydrogel.
10. The method for preparing photo-thermal dual-regulation smart glass according to claim 1, wherein the size of the glass is as follows: float glass having a length and width of 10cm × 10cm and a thickness of 3 mm.
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