CN108864332B - Linear double-branched azobenzene polymer and preparation method and application thereof - Google Patents
Linear double-branched azobenzene polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a linear double-branched azobenzene polymer and a preparation method and application thereof, wherein double-branched azobenzene is grafted on a side chain of polymethacrylic acid in a chemical bond mode to obtain the linear double-branched azobenzene polymer, the number average molecular weight of the linear double-branched azobenzene polymer is 18000-220000, the energy density is 130-150Wh/Kg, the half-life period is 850-950h, and the preparation method of the linear double-branched azobenzene polymer comprises the following steps: 1) amino protection, 2) preparation of amino-protected double-branched azobenzene, and 3) preparation of a double-branched azobenzene polymer.
Description
Technical Field
The invention relates to the technical field of composite functional materials, in particular to a linear double-branched azobenzene polymer, a preparation method and application thereof, and the linear double-branched azobenzene polymer has wide application prospects in the field of solar energy storage.
Background
As the energy consumption continues to accelerate, the need for alternative energy types is becoming more stringent. Solar energy exhibits a potential aspect because the annual consumption of solar energy at the earth's surface is only 0.1% of the total amount of energy impinging on the earth's surface. Solar thermal fuel cells can achieve chemical energy storage when absorbed solar energy is capable of transforming a substance from a stable heterogeneous state to a metastable state. And the stored solar energy may be released as heat by heating or catalytic stimulation. But provided that the lower energy state of the isomerized substance has the ability to absorb external energy. Burning deviceFuel cells are developed from portable battery technology with independent power grids. Currently, the three major photoisomerization pathways for solar fuel cells are: electrical cyclization reactions, reorientation of organometallic complexes, and isomerization of double bonds. Electrocyclic isomerization of, for example, (norbornadiene)<->Tetracycloheptane) can store a large amount of enthalpy (57kJ mol)-1) However, the organometallic (fulvalene) tetracarbonyl compound-ruthenium system exhibits a higher gravimetric energy density (30.6W h kg) due to synthesis difficulties or the occurrence of intermolecular chemical reactions at high concentrations hampering its use-1) But the use is limited because the raw materials are too expensive. In contrast, azo derivatives with reversible cis-trans photoisomerization properties show new promise for solar energy storage due to good stability, ease of synthesis and higher tunability of absorption frequencies.
One of the most important properties of azobenzene for energy storage is to improve the capacity of energy storage, and thus it is an effective method to increase the energy storage density of azo derivatives by calculation and experiment. The current method that has shown good results is to use carbon nanotubes, graphene or other hydrocarbons as a substrate, grafted on by chemical bonds, to increase the energy storage capacity by using the interaction between adjacent molecules during cis-trans isomerization. Although the azobenzene-carbon nanotube/azobenzene-graphene series has a high storage capacity, it is difficult to form a film due to its poor solubility, thus limiting its practical use in large quantities. The azobenzene polymer is formed by connecting azobenzene to a side chain through a chemical bond, and has the flexibility of the polymer while the intermolecular interaction of adjacent azobenzene is formed, so that the azobenzene polymer is favorable for film formation, and the azobenzene energy storage has higher competitiveness in practical application.
Disclosure of Invention
The invention aims to provide a linear double-branched azobenzene polymer and a preparation method thereof aiming at the technical defects in the prior art.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a linear double-branch azobenzene polymer is prepared through grafting double-branch azobenzene onto the side chain of polymethacrylic acid by chemical bond mode.
Preferably, the linear birthwort azobenzene polymer has the following structure:
in another aspect of the invention, the application of the linear double-branched azobenzene polymer in the energy storage material is also included, the number average molecular weight of the linear double-branched azobenzene polymer is 18000-220000, the energy density is 130-150Wh/Kg, and the half-life period is 850-950 h.
Preferably, the number average molecular weight of the linear double-branched azobenzene polymer is 19000-210000, the energy density is 135-145 Wh/Kg, and the half-life is 890-920 h.
In another aspect of the present invention, the preparation method of the linear birthwort azobenzene polymer comprises the following steps:
1) amino protection: dissolving 4-aminobenzoic acid and sodium nitrite in deionized water, slowly adding a hydrochloric acid aqueous solution into the deionized water, placing the mixture into an ice bath, stirring to prepare diazonium salt, slowly dripping the prepared diazonium salt solution into an aniline hydrochloric acid aqueous solution under the ice bath condition, adjusting the pH value to 6-7, stirring for 5-7H in the ice bath under the argon protection condition, reacting for 8-18H, washing the obtained crude product for multiple times by using deionized water and absolute ethyl alcohol, then using silica gel as a stationary phase, using ethyl acetate/n-hexane as an eluent for chromatographic separation, distilling the obtained components under reduced pressure and drying in vacuum to obtain 4- ((4-phenylaniline) diazenebenzoic acid, and adding the 4- ((4-phenylaniline) diazenebenzoic acid and NaOH into DMF/H2Dropwise adding di-tert-butyl dicarbonate into the O mixed solution under an ice bath condition, recovering to room temperature, continuing to react for 28-32 h, slowly dropwise adding HCl to the reaction product for acidification, dropwise adding deionized water into the reaction product, filtering the precipitate, repeatedly washing and drying the precipitate with deionized water and brine to obtain a solid, dissolving the product in dichloromethane, slowly dropwise adding oxalyl chloride into the dichloromethane, dropwise adding DMF into the mixture for reaction for 3-5h, and reacting the mixtureThe reaction solution is decompressed, rotary evaporated and dried and is dissolved in dichloromethane again;
2) preparing amino protected double-branched azobenzene: adding p-aminoazobenzene-4-sulfonic acid and N, N-diisopropylethylamine into dichloromethane, dropwise adding the solution into the dichloromethane, reacting for 8-18h, extracting the mixed solution with ammonium chloride solution, washing with dichloromethane continuously, mixing the obtained organic solvent layers, drying with anhydrous magnesium sulfate, filtering, distilling under reduced pressure, recrystallizing the crude product with DMF, dissolving the recrystallized product in methanol and trifluoroacetic acid, reacting for 8 hours at room temperature, removing the solvent by rotary evaporation, extracting for multiple times by using ethyl acetate, removing water by using anhydrous sodium sulfate, and drying in vacuum after rotary evaporation to obtain a product 4- ((4- (4- (- (4-aminobenzene) diazenyl) benzamido) phenyl) diazenyl) benzenesulfonic acid;
3) preparation of a birthwort azobenzene polymer: dissolving methacryloyl chloride liquid in dry CH in ice bath2Cl2Then dropwise adding the product obtained in step 2) to triethylamine and dried CH2Cl2After reaction at zero temperature for 20h, rotary evaporation, washing with dilute hydrochloric acid, sodium bicarbonate and sodium chloride solution, and reaction of the crude product with CH2Cl2Eluting in silica gel column, and recrystallizing the solution to obtain yellow monomer.
Dissolving the monomers, 2-cyanopropyl-2-ylbenzodithio and AIBN (azobisisobutyronitrile) in anisole, subjecting the solution to four freeze-thaw pump cycles and sealing under argon, reacting the polymerization system in an oil bath at 70-80 ℃ for 45-50h, dropping the polymerization solution into methanol, dissolving the precipitate in THF, removing the precipitate from the methanol, and removing unreacted monomers to obtain the final product.
Preferably, the molar ratio of the 4-aminobenzoic acid to the sodium nitrite in the step 1) is 1: 1-1: 1.1.
preferably, the molar ratio of the 4-aminobenzoic acid to the sodium nitrite in the step 1) is 1: 1-1: 1.1.
preferably, the molar ratio of 4-aminobenzoic acid to aniline in the step 1) is 1:1.
preferably, the molar ratio of 4- ((4-phenylaniline) diazenebenzoic acid to NaOH in the step 1) is 1: 1-1: 1.1.
Preferably, DMF and H in said step 1)2The volume ratio of O is 1:1.
preferably, the molar ratio of 4- ((4-phenylaniline) diazenebenzoic acid to di-tert-butyl dicarbonate in step 1) is 1:1.
Preferably, the molar ratio of 4- ((4-phenylaniline) diazenebenzoic acid to HCl in step 1) is 1.2: 1.
preferably, the molar ratio of the p-aminoazobenzene-4-sulfonic acid to the N, N-diisopropylethylamine in the step 2) is 1: 1.3.
preferably, the molar ratio of 4- ((4- (4- (- (4-aminobenzene) diazenyl) benzamido) phenyl) diazenyl) benzenesulfonic acid and methacryloyl chloride in step 3) is 1: 1.8.
Preferably, the molar ratio of triethylamine to methacryloyl chloride in the step 3) is 1: 1.8.
preferably, the molar ratio of 2-cyanopropyl-2-ylbenzodisulfide to monomer in step 3) is 1: 178.
preferably, the molar ratio of AIBN to monomer in step 3) is 1: 683.
Compared with the prior art, the invention has the beneficial effects that:
1. the linear double-branch azobenzene polymer of the invention has high energy and long half-life period when being used as an energy storage material.
2. The linear double-branched azobenzene polymer has high molecular weight, good flexibility and good film forming performance, and is convenient to popularize and apply as an energy storage material.
Drawings
FIG. 1 shows a process for preparing a linear birthwort azobenzene polymer according to the present invention.
FIG. 2 shows an ultraviolet-visible light absorption spectrum of the linear bisaliezo-benzene polymer obtained in example 2.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The reaction formula of the preparation method of the linear double-branched azobenzene polymer is shown in figure 1.
Example 1
1) 2.740g of 4-aminobenzoic acid and 1.380g of sodium nitrite were dissolved in 50ml of deionized water, and then 40ml of a 2mol/L aqueous hydrochloric acid solution was slowly added thereto and placed in an ice bath and stirred to prepare a diazonium salt. Slowly dropping the prepared diazonium salt solution into 20mmol aniline hydrochloric acid aqueous solution under the ice bath condition, adjusting the pH value to 6-7, stirring for 6 hours in the ice bath under the argon protection condition, and then reacting overnight. Washing the obtained crude product with deionized water and anhydrous ethanol for multiple times, and then performing chromatographic separation by using 5-micron silica gel as a stationary phase and ethyl acetate/n-hexane as an eluent. The resulting fraction was distilled under reduced pressure and dried in vacuo to give Azo (4- ((4-phenylaniline) diazenylbenzoic acid). 12mmol of Azo and 13mmol of NaOH were added to 30ml of 1:1DMF/H2And O is mixed in the solution. 12.5mmol of di-tert-butyl dicarbonate are added dropwise under ice-bath conditions. The reaction was allowed to return to room temperature and continued for 30 h. The reaction product was then acidified slowly dropwise with 5ml of 2M HCl and 30ml of deionized water were added dropwise thereto. The precipitate was filtered, washed repeatedly with deionized water and brine and dried to give a solid. 8.88mmol of the above product was dissolved in 40ml of dichloromethane, and 12.5mmol of oxalyl chloride was slowly added dropwise thereto. Then 250. mu.L of DMF was added dropwise to the mixture, and the reaction was carried out for 4 hours. The reaction solution was evaporated under reduced pressure to dryness and redissolved in 20ml of methylene chloride.
2) 9mmol of p-aminoazobenzene-4-sulfonic acid and 12mmol of N, N-diisopropylethylamine were added to 40ml of dichloromethane, and the solution was added dropwise to the above 20ml of dichloromethane and reacted overnight. The mixture was extracted with 100ml of ammonium chloride solution, washed with dichloromethane, and the resulting organic solvent layers were mixed, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The crude product was recrystallized from DMF. And finally, dissolving the product obtained by recrystallization in 12ml of methanol and 50ml of trifluoroacetic acid, reacting at room temperature for 8 hours, removing the solvent by rotary evaporation, extracting with ethyl acetate for multiple times, removing water by using anhydrous sodium sulfate, and drying in vacuum after rotary evaporation to obtain the product I.
3) Preparation of a birthwort azobenzene polymer: methacryloyl chloride liquid (1.986g,0.019mol) was dissolved in 10ml of dry CH under ice bath2Cl2Then added dropwise to product I (8.041g,0.016mol), triethylamine (1.624g,0.016mol) and dried CH2Cl2(50mL), after which the reaction was continued at zero degrees for 20 h. After rotary evaporation, washing with diluted hydrochloric acid, sodium bicarbonate and sodium chloride solution, and using CH to make the crude product2Cl2The solution was recrystallized by eluting on a silica gel column to give a yellow monomer (product II). The yield was 73%
The monomers (product II,2.337g,4.096mmol), 2-cyanopropyl-2-ylbenzodisulfide (5mg,0.023mmol), and AIBN (1mg,0.006mmol) were dissolved in anisole (4mL) after which the solution was subjected to four freeze-thaw pump cycles and sealed under argon. The polymerization system was reacted in an oil bath at 75 ℃ for 48 hours, after which the polymerization solution was dropped into methanol (40mL), the precipitate was dissolved in THF, the precipitate was removed from the methanol, and unreacted monomers were removed to obtain 1.923g of the final product III.
Example 2
1) 2.740g of 4-aminobenzoic acid and 1.380g of sodium nitrite were dissolved in 50ml of deionized water, and then 40ml of a 2mol/L aqueous hydrochloric acid solution was slowly added thereto and placed in an ice bath and stirred to prepare a diazonium salt. Slowly dropping the prepared diazonium salt solution into 20mmol aniline hydrochloric acid aqueous solution under the ice bath condition, adjusting the pH value to 6-7, stirring for 6 hours in the ice bath under the argon protection condition, and then reacting overnight. Washing the obtained crude product with deionized water and anhydrous ethanol for multiple times, and then performing chromatographic separation by using 5-micron silica gel as a stationary phase and ethyl acetate/n-hexane as an eluent. The resulting fraction was distilled under reduced pressure and dried in vacuo to give Azo. 12mmol of Azo and 13mmol of NaOH are added to 30ml of 1:1DMF/H2And O is mixed in the solution. 12.5mmol of di-tert-butyl dicarbonate are added dropwise under ice-bath conditions. The reaction was allowed to return to room temperature and continued for 30 h. The reaction product was then acidified slowly dropwise with 5ml of 2M HCl and 30ml of deionized water were added dropwise thereto. Filtering the precipitate, removing deionized water andthe solid is obtained by repeatedly washing and drying the brine. 8.88mmol of the above product was dissolved in 40ml of dichloromethane, and 12.5mmol of oxalyl chloride was slowly added dropwise thereto. Then 250. mu.L of DMF was added dropwise to the mixture, and the reaction was carried out for 4 hours. The reaction solution was evaporated under reduced pressure to dryness and redissolved in 20ml of methylene chloride.
2) 9mmol of p-aminoazobenzene-4-sulfonic acid and 12mmol of N, N-diisopropylethylamine were added to 40ml of dichloromethane, and the solution was added dropwise to the above 20ml of dichloromethane and reacted overnight. The mixture was extracted with 100ml of ammonium chloride solution, washed with dichloromethane, and the resulting organic solvent layers were mixed, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The crude product was recrystallized from DMF. Finally, the product obtained by recrystallization is dissolved in 12ml of methanol and 50ml of trifluoroacetic acid, reacted for 8h at room temperature, the solvent is removed by rotary evaporation, extracted with ethyl acetate for a plurality of times, and water is removed by anhydrous sodium sulfate, and the final product (product I) is obtained by vacuum drying after rotary evaporation.
3) Preparation of a birthwort azobenzene polymer: methacryloyl chloride liquid (1.986g,0.019mol) was dissolved in 10ml of dry CH under ice bath2Cl2Then added dropwise to product I (8.041g,0.016mol), triethylamine (1.624g,0.016mol) and dried CH2Cl2(50mL), after which the reaction was continued at zero degrees for 20 h. After rotary evaporation, washing with diluted hydrochloric acid, sodium bicarbonate and sodium chloride solution, and using CH to make the crude product2Cl2The solution was recrystallized by eluting on a silica gel column to give a yellow monomer (product II). The yield was 73%
The monomers (product II,2.337g,4.096mmol), 2-cyanopropyl-2-ylbenzodisulfide (5mg,0.023mmol), and AIBN (1mg,0.006mmol) were dissolved in anisole (4mL) after which the solution was subjected to four freeze-thaw pump cycles and sealed under argon. The polymerization system was reacted in an oil bath at 75 ℃ for 48h after which the polymerization solution was dropped into methanol (40mL), the precipitate was dissolved in THF, the precipitate was removed from the methanol, and unreacted monomers were removed to give 1.857g of the final product III.
Example 3
1) 2.740g of 4-aminobenzoic acid and 1.380g of sodium nitrite were dissolved in 50ml ofTo deionized water, 40ml of a 2mol/L aqueous hydrochloric acid solution was slowly added thereto and placed in an ice bath with stirring to prepare a diazonium salt. Slowly dropping the prepared diazonium salt solution into 20mmol aniline hydrochloric acid aqueous solution under the ice bath condition, adjusting the pH value to 6-7, stirring for 6 hours in the ice bath under the argon protection condition, and then reacting overnight. Washing the obtained crude product with deionized water and anhydrous ethanol for multiple times, and then performing chromatographic separation by using 5-micron silica gel as a stationary phase and ethyl acetate/n-hexane as an eluent. The resulting fraction was distilled under reduced pressure and dried in vacuo to give Azo. 12mmol of Azo and 13mmol of NaOH are added to 30ml of 1:1DMF/H2And O is mixed in the solution. 12.5mmol of di-tert-butyl dicarbonate are added dropwise under ice-bath conditions. The reaction was allowed to return to room temperature and continued for 30 h. The reaction product was then acidified slowly dropwise with 5ml of 2M HCl and 30ml of deionized water were added dropwise thereto. The precipitate was filtered, washed repeatedly with deionized water and brine and dried to give a solid. 8.88mmol of the above product was dissolved in 40ml of dichloromethane, and 12.5mmol of oxalyl chloride was slowly added dropwise thereto. Then 250. mu.L of DMF was added dropwise to the mixture, and the reaction was carried out for 4 hours. The reaction solution was evaporated under reduced pressure to dryness and redissolved in 20ml of methylene chloride.
2) 9mmol of p-aminoazobenzene-4-sulfonic acid and 12mmol of N, N-diisopropylethylamine were added to 40ml of dichloromethane, and the solution was added dropwise to the above 20ml of dichloromethane and reacted overnight. The mixture was extracted with 100ml of ammonium chloride solution, washed with dichloromethane, and the resulting organic solvent layers were mixed, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The crude product was recrystallized from DMF. Finally, the product obtained by recrystallization is dissolved in 12ml of methanol and 50ml of trifluoroacetic acid, reacted for 8h at room temperature, the solvent is removed by rotary evaporation, extracted with ethyl acetate for a plurality of times, and water is removed by anhydrous sodium sulfate, and the final product (product I) is obtained by vacuum drying after rotary evaporation.
3) Preparation of a birthwort azobenzene polymer: methacryloyl chloride liquid (1.986g,0.019mol) was dissolved in 10ml of dry CH under ice bath2Cl2Then added dropwise to product I (8.041g,0.016mol), triethylamine (1.624g,0.016mol) and dried CH2Cl2(50mL) and then reacted inAt zero degrees for 20 h. After rotary evaporation, washing with diluted hydrochloric acid, sodium bicarbonate and sodium chloride solution, and using CH to make the crude product2Cl2The solution was recrystallized by eluting on a silica gel column to give a yellow monomer (product II). The yield was 73%
The monomers (product II,2.337g,4.096mmol), 2-cyanopropyl-2-ylbenzodisulfide (5mg,0.023mmol), and AIBN (1mg,0.006mmol) were dissolved in anisole (4mL) after which the solution was subjected to four freeze-thaw pump cycles and sealed under argon. The polymerization system was reacted in an oil bath at 75 ℃ for 48h, after which the polymerization solution was dropped into methanol (40mL), the precipitate was dissolved in THF, the precipitate was removed from the methanol, and unreacted monomers were removed to obtain 1.936g of the final product III.
The results of the tests of the performance parameters of the three products of examples 1 to 3 are as follows:
1. the Energy density was measured by DSC (Saydjari AK, Weis P, Wu S. spaning the SolarSpectrum: Azo Polymer Solar Thermal Fuels for Simultaneous UV and VisibleLight Storage [ J ] Advanced Energy Materials,2016.) as shown in the above table, the Energy density stabilized at around 134- & 141Wh/Kg, indicating that the above linear, double-branched azobenzene polymer has a good ability to store Energy.
2. The half-life is measured according to ultraviolet-visible time spectroscopy (Zhao X, Feng Y, Qin C, et. control heat release from close-packed bis 4-Azo-reduced graphene oxide film for high-energy solid-state photothermal gases [ J ]. ChemSusChem, 2016). as shown in the above table, when the linear double-branched azobenzene polymer of the present invention is used for energy storage, the half-life is about 900h, and good controllability is achieved;
3. the number average molecular weight is measured by gel chromatography, the molecular weight is about 200000, the linear double-branch azobenzene polymer of the invention has high molecular weight, can greatly improve the flexibility and has good film-forming property.
The ultraviolet-visible light absorption spectrum of the linear-hyperbranched azobenzene polymer of example 2 was measured to obtain fig. 2, from which it can be seen that the linear-hyperbranched azobenzene polymer of the present invention has responsiveness to ultraviolet light.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of a linear double-branched azobenzene polymer is characterized by comprising the following steps: comprises the following steps
1) Amino protection: dissolving 4-aminobenzoic acid and sodium nitrite in deionized water, slowly adding a hydrochloric acid aqueous solution into the deionized water, placing the mixture into an ice bath, stirring to prepare diazonium salt, slowly dripping the prepared diazonium salt solution into an aniline hydrochloric acid aqueous solution under the ice bath condition, adjusting the pH value to 6-7, stirring for 5-7H in the ice bath under the argon protection condition, reacting for 8-18H, washing the obtained crude product for multiple times by using deionized water and absolute ethyl alcohol, then using silica gel as a stationary phase, using ethyl acetate/n-hexane as an eluent for chromatographic separation, distilling the obtained components under reduced pressure and drying in vacuum to obtain 4- (4-phenylaniline) diazenebenzoic acid, adding the 4- (4-phenylaniline) diazenebenzoic acid and NaOH into DMF/H2Dropwise adding di-tert-butyl dicarbonate into the O mixed solution under an ice bath condition, recovering to room temperature, continuing to react for 28-32 h, slowly dropwise adding HCl to the reaction product for acidification, dropwise adding deionized water into the reaction product, filtering the precipitate, repeatedly washing and drying the precipitate with deionized water and brine to obtain a solid, dissolving the product in dichloromethane, slowly dropwise adding oxalyl chloride into the mixture, dropwise adding DMF into the mixture for reaction for 3-5h, decompressing, rotary-steaming and drying the reaction solution, and re-dissolving the reaction solution in dichloromethane;
2) preparing amino protected double-branched azobenzene: adding p-aminoazobenzene-4-sulfonic acid and N, N-diisopropylethylamine into dichloromethane, dropwise adding the solution into the dichloromethane, reacting for 8-18h, extracting the mixed solution with ammonium chloride solution, washing with dichloromethane continuously, mixing the obtained organic solvent layers, drying with anhydrous magnesium sulfate, filtering, distilling under reduced pressure, recrystallizing the crude product with DMF, dissolving the recrystallized product in methanol and trifluoroacetic acid, reacting for 8 hours at room temperature, removing the solvent by rotary evaporation, extracting for multiple times by using ethyl acetate, removing water by using anhydrous sodium sulfate, and drying in vacuum after rotary evaporation to obtain a product 4- ((4- (4- (- (4-aminobenzene) diazenyl) benzamido) phenyl) diazenyl) benzenesulfonic acid;
3) preparation of a birthwort azobenzene polymer: dissolving methacryloyl chloride liquid in dry CH in ice bath2Cl2Then dropwise adding the product obtained in step 2) to triethylamine and dried CH2Cl2After reaction at zero temperature for 20h, rotary evaporation, washing with dilute hydrochloric acid, sodium bicarbonate and sodium chloride solution, and reaction of the crude product with CH2Cl2Eluting in a silica gel column, and recrystallizing the solution to obtain a yellow monomer;
the monomers, 2-cyanopropyl-2-ylbenzodithio and AIBN (azobisisobutyronitrile) are dissolved in anisole, after which the solution is subjected to four freeze-thaw pump cycles and is sealed under argon, the polymerization system is reacted in an oil bath at 70-80 ℃ for 45-50h, after which the polymerization solution is dropped into methanol, the precipitate is dissolved in THF, the precipitate is removed from the methanol, and the unreacted monomers are removed to give the final product.
2. The method for preparing a linear birthwort azobenzene polymer according to claim 1, wherein: the molar ratio of the 4-aminobenzoic acid to the sodium nitrite in the step 1) is 1: 1-1: 1.1; the molar ratio of the 4-aminobenzoic acid to the sodium nitrite in the step 1) is 1: 1-1: 1.1; the mol ratio of the 4-aminobenzoic acid to the aniline in the step 1) is 1: 1; the molar ratio of the 4- ((4-phenylaniline) diazenylbenzoic acid to the NaOH in the step 1) is 1: 1-1: 1.1; DMF and H in the step 1)2The volume ratio of O is 1: 1; the steps areThe molar ratio of 4- ((4-phenylaniline) diazenebenzoic acid to di-tert-butyl dicarbonate in step 1) is 1: 1; the molar ratio of 4- ((4-phenylaniline) diazenylbenzoic acid to HCl in the step 1) is 1.2: 1.
3. the method for preparing a linear birthwort azobenzene polymer according to claim 1, wherein: in the step 2), the molar ratio of the p-aminoazobenzene-4-sulfonic acid to the N, N-diisopropylethylamine is 1: 1.3.
4. the method for preparing a linear birthwort azobenzene polymer according to claim 1, wherein: the molar ratio of 4- ((4- (4- (- (4-aminophenyl) diazenyl) benzamido) phenyl) diazenyl) benzenesulfonic acid to methacryloyl chloride in the step 3) is 1: 1.8; the molar ratio of triethylamine to methacryloyl chloride in the step 3) is 1: 1.8.
5. the method for preparing a linear birthwort azobenzene polymer according to claim 1, wherein: the molar ratio of the 2-cyanopropyl-2-ylbenzodisulfide to the monomer in the step 3) is 1: 178.
6. the method for preparing a linear birthwort azobenzene polymer according to claim 1, wherein: the molar ratio of AIBN to monomer in step 3) is 1: 683.
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| US5314976A (en) * | 1992-04-13 | 1994-05-24 | National Science Council | Photo-responsive conductive polymers and the processes of making the same |
| CN101012182A (en) * | 2006-12-31 | 2007-08-08 | 苏州大学 | Azo monomer and polymer with third order non-linear optical property |
| CN106432567A (en) * | 2016-09-14 | 2017-02-22 | 天津大学 | Preparation method of polymer heat-storage material containing both-branch Azobenzene side groups |
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| US5314976A (en) * | 1992-04-13 | 1994-05-24 | National Science Council | Photo-responsive conductive polymers and the processes of making the same |
| CN101012182A (en) * | 2006-12-31 | 2007-08-08 | 苏州大学 | Azo monomer and polymer with third order non-linear optical property |
| CN106432567A (en) * | 2016-09-14 | 2017-02-22 | 天津大学 | Preparation method of polymer heat-storage material containing both-branch Azobenzene side groups |
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| "Controlling Heat Release from a Close‐Packed Bisazobenzene–Reduced‐Graphene‐Oxide Assembly Film for High‐Energy Solid‐State Photothermal Fuels";Xiaoze Zhao等;《CHEMSUSCHEM》;20161212;第10卷(第7期);第1395-1404页 * |
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