CN112111032B - Semi-main-chain azobenzene photo-thermal energy storage polymer and preparation method and application thereof - Google Patents
Semi-main-chain azobenzene photo-thermal energy storage polymer and preparation method and application thereof Download PDFInfo
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- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 238000004146 energy storage Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000835 fiber Substances 0.000 claims abstract description 10
- 239000004744 fabric Substances 0.000 claims abstract description 9
- 238000010146 3D printing Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 21
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 238000002390 rotary evaporation Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- DEKPYXUDJRABNK-UHFFFAOYSA-N dimethyl 5-aminobenzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC(N)=CC(C(=O)OC)=C1 DEKPYXUDJRABNK-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 238000005286 illumination Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000011084 recovery Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000007699 photoisomerization reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
- C08F122/22—Esters containing nitrogen
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- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S60/00—Arrangements for storing heat collected by solar heat collectors
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a semi-main-chain type azobenzene photothermal energy storage polymer, a preparation method and application thereof, and the semi-main-chain type azobenzene photothermal energy storage polymer can be used for 3D printing photothermal energy storage fibers and fabrics, and the 3D printing photothermal energy storage fibers and fabrics are applied to the technical field of space photothermal conversion and heating of spacecrafts. The semi-main chain type azobenzene photo-thermal energy storage polymer has a structure shown as the following formula:
Description
Technical Field
The invention relates to the technical field of photo-thermal energy storage, in particular to a semi-main-chain type azobenzene photo-thermal energy storage polymer and a preparation method and application thereof.
Background
With the rapid development of human industrialization, the demand for energy consumption is increasing. Fossil fuels as a primary energy source are often associated with cost and environmental concerns. Nowadays, much attention is paid to the utilization of renewable energy sources such as solar energy, wind energy and heat energy, and the renewable energy sources replace traditional fossil fuel energy sources. Since solar energy is the most abundant renewable energy, the direct conversion of solar energy into thermal energy has attracted great attention. Although there are several large-scale solar energy collection and storage solutions developed (e.g., large area solar cells), the application of solar energy to small devices for industrial and consumer use remains a significant challenge. Closed cycle systems, for example, employing recyclable energy storage on the bonds of organic chromophores, offer a unique advantage in that both energy capture and storage are in the same material. Furthermore, in some applications, thermal energy may be required rather than electrical energy, and these photothermal materials have great potential in these applications. Azobenzene is a convertible compound with reversible cis-trans photoisomerization capability. The optical response material containing azobenzene has wide application in the fields of information storage, photoetching, solar energy storage, optical switch porous material, driver, photopharmacology and the like. The energy difference between the cis-trans isomer of azobenzene is about 50kJ/mol, while the energy difference between the trans isomer and the excited state is about 200 kJ/mol. The characteristic can realize the storage of light energy and the release in the form of heat, and realize the storage of photo-thermal energy. The light-controllable azophenyl polymer has poor reusability, such as energy attenuation after only a few energy conversions and releases in photothermal conversion and release cycles, and other properties such as low energy density, poor thermal stability, too short half-life, etc. are not satisfactory for practical purposes. In order to further promote the application of the azophenyl polymer material in the field of photothermal conversion, more advanced polymer molecule design is urgently needed to promote the preparation of intelligent photothermal energy storage fibers and fabrics.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a semi-main-chain type azobenzene photothermal energy storage polymer, and a preparation method and an application thereof, wherein the prepared azobenzene photothermal energy storage polymer has a higher energy density and a shorter half-life period, and can be made into fibers and fabrics with different shapes by 3D printing.
The invention provides a semi-main chain type azobenzene photo-thermal energy storage polymer, which has a structure shown in a formula I:
formula I semi-main chain type azobenzene photo-thermal energy storage polymer
The semi-main chain type azobenzene photo-thermal energy storage polymer main chain contains one benzene ring of azobenzene, and N ═ N and the other benzene ring are used as polymer branched chains. Compared with the conventional branched chain type or main chain type azobenzene polymer, the semi-main chain type azobenzene photo-thermal energy storage polymer has the advantages that the template effect of the main chain is enhanced on the main chain by one benzene ring, and the integral rigidity is reduced, so that the unimolecular energy value and the recovery half-life period are greatly improved. Meanwhile, the polymer film forming property and the processability are enhanced because the polymer units have flexible chains.
Experimental results show that the molecular azobenzene unit of the semi-main-chain azobenzene photo-thermal energy storage polymer can realize trans → cis isomerism under the illumination of 260-430nm wavelength. The heat can be released under the illumination of 490-600nm wavelength, and the energy density is as high as 53-72 Wh/kg.
When the molecule is heated to 51-78 ℃ under the illumination of 490-600nm wavelength, the heat can be released rapidly for 3-15 min; at low temperature, such as-10-5 deg.C, heat can be slowly released.
The invention also provides a preparation method of the semi-main chain type azobenzene photo-thermal energy storage polymer, which comprises the following steps:
preparation of dimethyl 3, 5-azoisophthalate.
Preparation of 3, 5-azoisophthalic acid.
3. And (3) preparing a semi-main chain type azobenzene photo-thermal energy storage polymer monomer in a formula III.
4. Polymerizing semi-main chain azobenzene polymer.
In some embodiments of the present invention, taking the feeding amount of the dimethyl 5-aminoisophthalate as 2.1g to 2.52g as an example, the preparation method specifically comprises:
(1) preparation of dimethyl 3, 5-azoisophthalate.
A mixture of dimethyl 5-aminoisophthalate (2.1 g-2.52 g, 10-12 mmol), nitrosobenzene (1.067 g-1.28 g, 10-12 mmol) and glacial acetic acid (80-90 ml) in a 250ml round bottom flask was stirred in an oil bath at 40 ℃ for 1 day. After cooling the solution, the resulting mixture was slowly added to saturated NaHCO3In solution, no yellow precipitate formed until stirring. The orange precipitate was filtered, washed with distilled water (3X 30ml) and then dried in air to obtain 1.43g (48% based on dimethyl 5-aminoisophthalate) of dimethyl 3, 5-azoisophthalate of the formula II.
3, 5-azoisophthalic acid of the formula II
(2) Preparation of 3, 5-azoisophthalic acid.
A mixture of dimethyl azoisophthalate (1.49g, 5mmol) and tetrahydrofuran THF, ethanol, 20% NaOH (15ml/15ml/15ml) was added to a 100-flask and stirred at reflux overnight. After removing the organic phase, 1M HCl solution was added so that the pH became 2.0 to 3.0 to obtain an orange precipitate. After stirring for 1 hour, the orange precipitate was filtered and washed with distilled water (3X 30ml) to give 1.24g (yield 92%) of 3, 5-azoisophthalic acid as a product.
(3) Preparing a semi-main chain type azobenzene photo-thermal energy storage polymer monomer shown in a formula II.
3, 5-azo isophthalic acid (1.3512g, 5mmol) is dissolved in 80-100ml acetonitrile, 5.0-5.2ml oxalyl chloride (about 1.2 equiv) and 30-50. mu.L DMF are added under the protection of inert gas (argon), and reaction is carried out for 3-5h at normal temperature. Excess oxalyl chloride and solvent are removed by vacuum rotary evaporation, the residual solid is dissolved in 50ml tetrahydrofuran, 5.2-5.3ml 3-butylene-1 alcohol is added under the protection of argon, and the reaction is carried out for 8 hours at 40 ℃ in the dark. After the reaction, the solvent and excess 3-buten-1 ol were removed by rotary evaporation in vacuo, and the product was washed with deionized water to obtain 1.435g of an orange solid product, i.e., a monomer represented by formula II.
(4) Polymerizing semi-main chain azobenzene polymer.
Polymerization of semi-main chain azobenzene: reacting monomers with n-butylamine in a ratio of 1: 1, 2% by mass of photoinitiator I651 and 5ml of tetrahydrofuran are added and mixed homogeneously on a vortex mixer. Then reflux reaction is carried out for 6h at 70 ℃, and the solvent is removed by vacuum rotary evaporation to obtain a viscous oligomer precursor. The precursor can be photopolymerized into a semi-main chain type azobenzene polymer shown in a formula I under the irradiation of ultraviolet light.
The invention provides an application of the semi-main chain type azobenzene photo-thermal energy storage polymer or the semi-main chain type azobenzene photo-thermal energy storage polymer prepared by the preparation method as solar thermal fuel, 3D printing fibers and fabrics.
The solar thermal fuel, the fiber and the fabric can be applied to the technical field of space light driving and heating of spacecrafts.
Compared with the prior art, the main chain of the semi-main chain type azobenzene photothermal energy storage polymer contains one benzene ring of azobenzene, and N ═ N and the other benzene ring are used as polymer branched chains. Compared with the conventional branched chain type or main chain type azobenzene polymer, the semi-main chain type azobenzene photo-thermal energy storage polymer has the advantages that the template effect of the main chain is enhanced on the main chain by one benzene ring, and the integral rigidity is reduced, so that the unimolecular energy value and the recovery half-life period are greatly improved. Meanwhile, the polymer film forming property and the processability are enhanced because the polymer units have flexible chains. The prepared azobenzene photothermal energy storage polymer has higher energy density and shorter half life, and can be made into fibers and fabrics with different shapes through 3D printing.
Drawings
FIG. 1 is an infrared spectrum of a semi-main chain type azobenzene photothermal energy storage polymer monomer prepared in example 1.
FIG. 2 is a diagram showing the isomerization recovery of the ultraviolet absorption spectrum of the semi-main-chain azobenzene photo-thermal energy storage polymer after being irradiated by 490-600nm light.
FIG. 3 is a DSC of semi-backbone azobenzene photothermal energy storage polymer prepared in example 1.
Detailed Description
The invention provides a semi-main-chain azobenzene photo-thermal energy storage polymer, a preparation method and application thereof, and the semi-main-chain azobenzene photo-thermal energy storage polymer has a structure shown in a formula I. The structural unit of the azobenzene polymer comprises azobenzene molecules, wherein one benzene ring of the azobenzene is arranged on a polymer main chain, the other benzene ring is arranged on a polymer side chain, and energy can be stored when the trans-form is converted into the cis-form by utilizing the energy difference between the two configurations of the azobenzene units, otherwise, heat can be released. The special molecular structure enhances the template effect of a polymer chain, the main chain type and branched chain type azobenzene polymers are greatly improved in the aspects of energy density value and recovery half-life compared with the traditional main chain type and branched chain type azobenzene polymers, photo-thermal energy storage fibers can be prepared through 3D printing and woven into different shapes, and finally, the controllable release of heat energy is realized by utilizing illumination and heating, so that the solar energy is fully utilized to carry out photo-thermal energy conversion and storage, and the polymer chain is used as a solar energy fuel to be applied to the technical field of space light control driving and heating of a new-generation spacecraft.
In order to further illustrate the present invention, the following will describe in detail the azophenyl photothermal energy storage molecule, its preparation method and application.
Example 1
(1) Preparation of dimethyl 3, 5-azoisophthalate.
A mixture of dimethyl 5-aminoisophthalate (2.2g), nitrosobenzene (1.15g) and glacial acetic acid (85ml) in a 250ml round bottom flask was stirred in an oil bath at 40 ℃ for 1 day. After cooling the solution, the resulting mixture was slowly added to saturated NaHCO3In solution, no yellow precipitate formed until stirring. The orange precipitate was filtered, washed with distilled water (3X 30ml), and then dried in the air to give 1.48g of dimethyl 3, 5-azoisophthalate.
(2) Preparation of 3, 5-azoisophthalic acid.
A mixture of dimethyl 3, 5-azoisophthalate (1.49g, 5mmol) and tetrahydrofuran THF, ethanol, 20% NaOH (15ml/15ml/15ml) was added to a 100ml flask and stirred under reflux overnight. After removing the organic phase, 1M HCl solution was added so that the pH became 2.0 to 3.0 to obtain an orange precipitate. After stirring for 1 hour, the orange precipitate was filtered and washed with distilled water (3X 30ml) to give 1.24g (yield 92%) of 3, 5-azoisophthalic acid as a product.
(3) And (3) preparing a semi-main chain type azobenzene photo-thermal energy storage polymer monomer in a formula III.
3, 5-azo isophthalic acid (1.3512g, 5mmol) is dissolved in 80-100ml acetonitrile, and 5.0-5.2ml oxalyl chloride (about 1.2 equiv) and 30-50. mu.L N, N-dimethylformamide DMF are added under the protection of inert gas (argon) to react for 3-5h at normal temperature. Excess oxalyl chloride and solvent are removed by vacuum rotary evaporation, the residual solid is dissolved in 50ml tetrahydrofuran, 5.2-5.3ml 3-butylene-1 alcohol is added under the protection of argon, and the reaction is carried out for 8 hours at 40 ℃ in the dark. After the reaction, the solvent and the excess 3-buten-1 ol were removed by vacuum rotary evaporation, and the product was washed with deionized water to obtain 1.435g of an orange solid product, i.e., a monomer represented by formula III.
Formula III semi-main chain type azobenzene photo-thermal energy storage polymer monomer
(4) Polymerizing semi-main chain azobenzene polymer.
Polymerization of semi-main chain azobenzene: reacting monomers with n-butylamine in a ratio of 1: 1, 2% by mass of photoinitiator I651 and 5ml of tetrahydrofuran are added and mixed homogeneously on a vortex mixer. Then reflux reaction is carried out for 6h at 70 ℃, and the solvent is removed by vacuum rotary evaporation to obtain a viscous oligomer precursor. The precursor can be photopolymerized into a semi-main chain type azobenzene polymer shown in a formula I under the irradiation of ultraviolet light.
The energy density was determined to be 68 Wh/kg.
The prepared azophenyl photo-thermal energy storage material is illuminated at 490-600nm, and the ultraviolet absorption spectrum isomerization recovery graph is shown in figure 1, wherein a curve a is an illumination 2min curve, a curve b is an illumination 6min curve, and a curve c is an illumination 10min curve.
The structure was examined by infrared spectroscopy and the results are shown in FIG. 1.
As can be seen from FIG. 2, the cis-tridentate azobenzene material has cis → trans isomerization and ultraviolet absorption change under the illumination of 490-600nm wavelength. It can be seen that with increasing illumination time, the trans characteristic absorption peak is significantly enhanced, indicating a cis-to-trans reversion.
The curve c to a is the structure recovery after 1min to 10min, the change trend is that the trans characteristic absorption peak is obviously enhanced, and the recovery from cis form to trans form is marked, which shows that the half-life period of the cis-trilobal azobenzene material is 10min and shorter.
The exotherm was measured by differential scanning calorimetry and the DSC chart is shown in FIG. 2.
As can be seen from FIG. 2, the exothermic curve of the trinuclear azobenzene material Differential Scanning Calorimeter (DSC), B is a first heating curve, an obvious exothermic peak can be seen, D is a first cooling curve, F is a second heating curve, and no exothermic peak can be seen.
Example 2
(1) Preparation of dimethyl 3, 5-azoisophthalate.
A mixture of dimethyl 5-aminoisophthalate (2.3g), nitrosobenzene (1.2g) and glacial acetic acid (90ml) in a 250ml round bottom flask was stirred in an oil bath at 40 ℃ for 1 day. After cooling the solution, the resulting mixture was slowly added to saturated NaHCO3In solution, no yellow precipitate formed until stirring. The orange precipitate was filtered, washed with distilled water (3X 30ml), and then dried in the air to give 1.41g of dimethyl 3, 5-azoisophthalate.
(2) Preparation of 3, 5-azoisophthalic acid.
A mixture of dimethyl azoisophthalate (1.49g, 5mmol) and tetrahydrofuran THF, ethanol, 20% NaOH (15ml/15ml/15ml) was added to a 100-flask and stirred at reflux overnight. After removing the organic phase, 1M HCl solution was added so that the pH became 2.0 to 3.0 to obtain an orange precipitate. After stirring for 1 hour, the orange precipitate was filtered and washed with distilled water (3X 30ml) to give 1.24g (yield 92%) of 3, 5-azoisophthalic acid as a product.
(3) And (3) preparing a semi-main chain type azobenzene photo-thermal energy storage polymer monomer in a formula III.
3, 5-azo isophthalic acid (1.3512g, 5mmol) is dissolved in 80-100ml acetonitrile, 5.0-5.2ml oxalyl chloride (about 1.2 equiv) and 30-50. mu.L DMF are added under the protection of inert gas (argon), and reaction is carried out for 3-5h at normal temperature. Excess oxalyl chloride and solvent are removed by vacuum rotary evaporation, the residual solid is dissolved in 50ml tetrahydrofuran, 5.2-5.3ml 3-butylene-1 alcohol is added under the protection of argon, and the reaction is carried out for 8 hours at 40 ℃ in the dark. After the reaction, the solvent and the excess 3-buten-1 ol were removed by vacuum rotary evaporation, and the product was washed with deionized water to obtain 1.435g of an orange solid product, i.e., a monomer represented by formula III.
(4) Polymerizing semi-main chain azobenzene polymer.
Polymerization of semi-main chain azobenzene: reacting monomers with n-butylamine in a ratio of 1: 1, 2% by mass of photoinitiator I651 and 5ml of tetrahydrofuran are added and mixed homogeneously on a vortex mixer. Then reflux reaction is carried out for 6h at 70 ℃, and the solvent is removed by vacuum rotary evaporation to obtain a viscous oligomer precursor. The precursor can be photopolymerized into a semi-main chain type azobenzene polymer shown in a formula I under the irradiation of ultraviolet light.
The energy density was found to be 64 Wh/kg.
Example 3
(1) Preparation of dimethyl 3, 5-azoisophthalate.
A mixture of dimethyl 5-aminoisophthalate (2.2g), nitrosobenzene (1.15g) and glacial acetic acid (85ml) in a 250ml round bottom flask was stirred in an oil bath at 40 ℃ for 1 day. After cooling the solution, the resulting mixture was slowly added to saturated NaHCO3In solution, no yellow precipitate formed until stirring. The orange precipitate was filtered, washed with distilled water (3X 30ml), and then dried in the air to give 1.48g of dimethyl 3, 5-azoisophthalate.
(2) Preparation of 3, 5-azoisophthalic acid.
A mixture of dimethyl azoisophthalate (1.49g, 5mmol) and tetrahydrofuran THF, ethanol, 20% NaOH (15ml/15ml/15ml) was added to a 100ml flask and stirred at reflux overnight. After removing the organic phase, 1M HCl solution was added so that the pH became 2.0 to 3.0 to obtain an orange precipitate. After stirring for 1 hour, the orange precipitate was filtered and washed with distilled water (3X 30ml) to give 1.24g (yield 92%) of 3, 5-azoisophthalic acid as a product.
(3) Preparing a main chain type azobenzene photo-thermal energy storage polymer monomer shown in a formula III.
3, 5-azo isophthalic acid (1.3512g, 5mmol) is dissolved in 80-100ml acetonitrile, 5.0-5.2ml oxalyl chloride (about 1.2 equiv) and 30-50. mu.L DMF are added under the protection of inert gas (argon), and reaction is carried out for 3-5h at normal temperature. Excess oxalyl chloride and solvent are removed by vacuum rotary evaporation, the residual solid is dissolved in 50ml tetrahydrofuran, 5.2-5.3ml 3-butylene-1 alcohol is added under the protection of argon, and the reaction is carried out for 8 hours at 40 ℃ in the dark. After the reaction, the solvent and the excess 3-buten-1 ol were removed by vacuum rotary evaporation, and the product was washed with deionized water to obtain 1.435g of an orange solid product, i.e., a monomer represented by formula III.
(4) Polymerizing semi-main chain azobenzene polymer.
Polymerization of semi-main chain azobenzene: reacting monomers with n-butylamine in a ratio of 1: 1, 2% by mass of photoinitiator I651 and 5ml of tetrahydrofuran are added and mixed homogeneously on a vortex mixer. Then reflux reaction is carried out for 6h at 70 ℃, and the solvent is removed by vacuum rotary evaporation to obtain a viscous oligomer precursor. The precursor can be photopolymerized into a semi-main chain type azobenzene polymer shown in a formula I under the irradiation of ultraviolet light.
The energy density was found to be 57 Wh/kg.
The embodiments show that the prepared azophenyl photothermal energy storage molecule has higher energy density and shorter half-life.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (8)
1. A semi-main chain type azobenzene photo-thermal energy storage polymer has a structure shown as the following formula:
2. a preparation method of a semi-main-chain azobenzene photo-thermal energy storage polymer comprises the following steps:
(1) preparation of dimethyl 3, 5-azoisophthalate: 5-Aminoisophthalic acid dimethyl ester, nitrosobenzene and glacial acetic acid are mixed homogeneously and the resulting mixture is added to saturated NaHCO3In solution, a yellow precipitate formed; filtering, washing and drying the orange precipitate to obtain 3, 5-azo dimethyl isophthalate;
(2)3, 5-azoisophthalic acid: preparing a mixed solution from Tetrahydrofuran (THF), ethanol and 20% NaOH with the same volume, adding dimethyl 3, 5-azoisophthalate into the mixed solution, fully mixing, adjusting the pH value to be 2.0-3.0 to obtain an orange precipitate, filtering, and washing the orange precipitate to obtain a product, namely 3, 5-azoisophthalic acid;
(3) preparing a semi-main chain type azobenzene photo-thermal energy storage polymer monomer: dissolving 3, 5-azoisophthalic acid in acetonitrile, adding more than 1.1 equivalent of oxalyl chloride under the protection of inert gas, adding DMF (dimethyl formamide), reacting at normal temperature, removing excessive oxalyl chloride and solvent by vacuum rotary evaporation, dissolving the residual solid in tetrahydrofuran, adding 3-buten-1 alcohol under the protection of inert gas, reacting at 40 ℃ in a dark place, removing the solvent and excessive 3-buten-1 alcohol by vacuum rotary evaporation after the reaction is finished, washing the product with deionized water to obtain an orange solid product, namely a semi-main chain azobenzene photothermal energy storage polymer monomer shown in the following formula:
(4) and (3) carrying out polymerization reaction on the semi-main chain type azobenzene.
3. The production method according to claim 2, wherein in the step (1), the mass-to-volume ratio of dimethyl 5-aminoisophthalate, nitrosobenzene and glacial acetic acid is (2.1g to 2.52 g): (1.067 g-1.28 g): (80-90 ml).
4. The method according to claim 2, wherein in the step (2), the orange precipitate is obtained from the preparation of 3, 5-azoisophthalic acid by adjusting the pH to 2.0 to 3.0 with 1M hydrochloric acid.
5. The method according to claim 2, wherein in the step (3), the ratio of 1.3512 g: 80-100ml of 3, 5-azoisophthalic acid is dissolved in acetonitrile.
6. The method according to claim 2, wherein in the step (4), the semi-main chain type azobenzene photothermal energy storage polymer monomer and n-butylamine are mixed in a ratio of 1: 1, adding 2% of photoinitiator and tetrahydrofuran, uniformly mixing on a vortex mixer, then carrying out reflux reaction at 70 ℃ for 6 hours, and carrying out vacuum rotary evaporation to remove the solvent to obtain a viscous oligomer precursor, wherein the precursor is subjected to photopolymerization under the irradiation of ultraviolet light to synthesize the semi-main chain azobenzene polymer shown in the formula I.
7. The semi-main chain type azobenzene photothermal energy storage polymer prepared according to the preparation method of claim 1 or the semi-main chain type azobenzene polymer prepared according to the preparation method of any one of claims 2 to 6 is used for 3D printing photothermal energy storage fibers and fabrics.
8. The use according to claim 7, wherein the 3D printed photothermal energy storage fibers and fabrics are used in the space photothermal conversion and heating technology field of spacecraft.
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| CN103159909A (en) * | 2013-03-22 | 2013-06-19 | 江苏大学 | Preparation method and application of main-chain-type chiral polymer thermal-photo switch material |
| CN104045754A (en) * | 2014-06-18 | 2014-09-17 | 北京科技大学 | Method for synthesizing visible-light response type azobenzene polymer |
| WO2020109855A1 (en) * | 2018-12-01 | 2020-06-04 | Ehsani Telgerafchi Armaghan | Fabrication of polymeric solar thermal fuel composites applicable as stff, stfi, steg, stfp |
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| CN103159909A (en) * | 2013-03-22 | 2013-06-19 | 江苏大学 | Preparation method and application of main-chain-type chiral polymer thermal-photo switch material |
| CN104045754A (en) * | 2014-06-18 | 2014-09-17 | 北京科技大学 | Method for synthesizing visible-light response type azobenzene polymer |
| WO2020109855A1 (en) * | 2018-12-01 | 2020-06-04 | Ehsani Telgerafchi Armaghan | Fabrication of polymeric solar thermal fuel composites applicable as stff, stfi, steg, stfp |
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