CN112831057B - Visible light response aryl azo pyrazole polymer and synthesis method thereof - Google Patents
Visible light response aryl azo pyrazole polymer and synthesis method thereof Download PDFInfo
- Publication number
- CN112831057B CN112831057B CN202110013945.7A CN202110013945A CN112831057B CN 112831057 B CN112831057 B CN 112831057B CN 202110013945 A CN202110013945 A CN 202110013945A CN 112831057 B CN112831057 B CN 112831057B
- Authority
- CN
- China
- Prior art keywords
- polymer
- aryl azo
- solution
- pyrazole
- arylazopyrazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
- C08G83/004—After treatment of dendrimers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
A visible light responding aryl azo pyrazole polymer and a synthesis method thereof. The aryl azo pyrazole polymer is prepared by carrying out Michael addition reaction on a methylthio para-substituted aryl azo pyrazole derivative and polyamide-amine (PAMAM) dendritic macromolecules. The aryl azo pyrazole polymer with the methylthio para-substituted aryl azo pyrazole is prepared by standard diazotization reaction, and the conversion from trans to cis isomer and the reversion process from cis to trans can be completed under the excitation of visible light. The synthetic method is simple and high in yield, the azo pyrazole functional group in the aryl-containing azo pyrazole polymer can realize high isomerization degree from trans to cis under the irradiation of purple light (405nm), and can realize rapid recovery from cis to trans under the irradiation of green light (520 nm). In addition, the cis isomer has a half-life of up to 13 days at room temperature under dark conditions. The method opens up a new way for developing novel visible light response functional polymer materials and molecular photo-thermal storage materials.
Description
Technical Field
The invention belongs to the field of light response functional polymers, and particularly relates to a visible light response aryl azo pyrazole polymer and a synthesis method thereof.
Background
The azobenzene compound is a photochromic molecule which can be isomerized from trans to cis under ultraviolet irradiation, and from cis to trans under green irradiation. Based on reversible photoisomerization, many researchers at home and abroad report many researches on grafting azobenzene into polymerization to prepare photoresponse functional polymers, and the researches make the azobenzene completely exposed in various technical fields such as optical switches, optical drive, energy and information storage and the like. However, the currently reported azobenzene derivatives are generally limited to complete trans-cis isomerization under ultraviolet irradiation, and the isomerization degree and half-life of azobenzene are to be improved, which greatly limits the wider application of photoresponsive polymer functions. To address this scientific challenge, pyrazolylazo compounds with extraordinary half-lives and high degrees of isomerization have been synthesized in recent years. However, such compounds are still limited to complete trans-to-cis conversion under uv light irradiation. Therefore, it is necessary to design and synthesize azo derivatives that can achieve reversible isomerization in the visible light band and have high isomerization degree and long half-life. In view of the above, the invention relates to a synthesis method of a visible-light-responsive aryl azo pyrazole polymer, thereby providing a new strategy for application of a light-responsive functional polymer under visible light irradiation.
Disclosure of Invention
The invention aims to provide a synthesis method of a visible-light-responsive aryl azo pyrazole polymer. The invention adopts the following technical scheme:
a visible-light responsive arylazopyrazole polymer characterized by: the aryl azo pyrazole derivative is covalently grafted on the surface of the dendritic polymer through Michael addition reaction, and the structural formula of the obtained aryl azo pyrazole polymer is as follows:
the synthesis method of the visible light response aryl azo pyrazole polymer comprises the following steps:
the method comprises the following steps: preparation of arylazopyrazoles: 4- (methylthio) aniline was dissolved in a mixed solution of concentrated hydrochloric acid and ethanol and cooled to 0 to 5 ℃. An aqueous solution of sodium nitrite was slowly added dropwise to the above solution and stirred for 1-2h to prepare a diazonium salt. Acetylacetone was added to a mixed solution of ethanol and water, followed by addition of sodium acetate and cooling to 0-5 ℃. The diazo solution is slowly added dropwise to the solution and the reaction is continued with stirring, the yellow precipitate obtained is filtered and washed with cold ethanol to give a yellow crude arylazoacetylacetone product. Dissolving aryl azoacetylacetone in ethanol, dropwise adding hydrazine hydrate into the ethanol, stirring and heating the mixed liquid to 60-80 ℃ under nitrogen atmosphere, and refluxing for 12-48 h. After completion of the reaction, it was cooled to room temperature, the solvent was concentrated and dissolved with dichloromethane, and washed with a saturated sodium chloride solution several times. The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain arylazopyrazole, which was finally purified by column chromatography.
Step two: preparation of arylazopyrazole derivatives: dissolving aryl azo pyrazole in acetonitrile, then sequentially adding 12-bromododecyl alcohol, potassium carbonate and potassium iodide, heating the mixed solution to 60-70 ℃ under the nitrogen atmosphere, and carrying out reflux reaction for 24-48 h. After completion of the reaction, the inorganic salts were removed by filtration and the filtrate was concentrated to dryness under reduced pressure, and then the aqueous phase was extracted by dissolving with dichloromethane. The organic layer was dried over anhydrous sodium sulfate and concentrated to give an intermediate product, which was finally purified by column chromatography to give the desired compound. Dissolving the obtained compound in anhydrous tetrahydrofuran, cooling to 0-5 ℃, adding triethylamine, adding a mixed solution of acryloyl chloride and the anhydrous tetrahydrofuran, and continuing stirring for 24-36 h. After the reaction is finished, filtering to remove triethylamine salt, concentrating to be dry, dissolving with dichloromethane, washing and extracting for multiple times by using a saturated sodium chloride solution, and completely removing the triethylamine salt and acryloyl chloride. The organic phase is dried over anhydrous sodium sulfate and concentrated to dryness, and finally purified by column chromatography to give the desired arylazopyrazole derivative.
Step three: preparation of aryl azo pyrazole polymer: the arylazopyrazole derivative (AAP) was dissolved in methanol sufficiently, and then a methanol solution of a third generation polyamidoamine dendrimer (G3) was slowly added dropwise. After the dropwise addition is finished, the mixed solution is placed in an oil bath at the temperature of 40-50 ℃ under the nitrogen atmosphere and stirred for reaction for 24-36 h. The reacted solution was poured into a large amount of cold diethyl ether to precipitate the product and remove the excess arylazopyrazole derivative. And drying the filtered solid at 40-45 ℃ for 30-36h in vacuum to obtain the dried azo polymer.
Further, in the first step, the molar ratio of 4- (methylthio) aniline to sodium nitrite to acetylacetone to sodium acetate is 1:1:1:2 to 1:3:3: 5; the volume ratio of the concentrated hydrochloric acid to the ethanol is 1: 2-1: 10; the volume ratio of the ethanol to the water is 1: 1-4: 1; the molar ratio of the aryl azo acetylacetone to the hydrazine hydrate is 1: 1-1: 6; the volume ratio of the dichloromethane to the saturated sodium chloride solution is 1: 2-1: 6.
Further, the number of times of the brine extraction in the first step is 2-6; developing agents used for column chromatography purification of the crude product are ethyl acetate and petroleum ether, and the volume ratio of the developing agents to the petroleum ether is 1: 1-1: 5.
Further, in the second step, the molar ratio of the aryl azo pyrazole to the potassium iodide to the potassium carbonate to the 12-bromododecyl alcohol is 2:1:5: 3-2: 3:12: 9; the molar ratio of the intermediate product to the triethylamine to the acryloyl chloride is 1:3: 3-1: 8: 9.
Further, the volume ratio of the dichloromethane to the saturated sodium chloride solution in the second step is 1: 2-1: 8; the washing times of the saturated sodium chloride solution are 2-5 times; developing agents used for intermediate product column chromatography purification are ethyl acetate and n-hexane, and the volume ratio of the developing agents to the n-hexane is 1: 1-3: 2; developing agents used for column chromatography purification of the aryl azo pyrazole derivative are ethyl acetate and petroleum ether, and the volume ratio of the developing agents is 1: 3-2: 1.
Further, the molar ratio of the polyamide-amine dendritic macromolecule to the aryl azo pyrazole derivative in the third step is 1: 30-1: 60; the volume ratio of the methanol to the ether is 1: 20-1: 40.
The key points of the technology of the invention are as follows: the aryl azo pyrazole with visible light absorption is prepared by standard diazotization reaction by using the aniline substituted by the methylthio as a raw material. Due to the strong electron donating ability of methylthio, the absorption wavelength of aryl azo pyrazole is red-shifted so as to realize the obvious absorption of visible light wave band. Compared with other azo heterocyclic derivatives which can only be isomerized by absorbing ultraviolet light, the novel aryl azo pyrazole has wider application prospect. In addition, the amplification of the aryl azo pyrazole on the surface of the polyamide-amine dendritic polymer can be realized by regulating and controlling the molar ratio of the aryl azo pyrazole and the polyamide-amine dendritic polymer.
In conclusion, the beneficial effects of the invention are as follows:
the aryl azo pyrazole polymer designed and synthesized by the invention can realize high isomerization degree from trans to cis and rapid recovery from cis to trans under the irradiation of visible light, and the storage half life of the cis isomer of the synthesized aryl azo pyrazole polymer under the dark condition at room temperature is as long as 13 days. In addition, the aryl azo pyrazole polymer designed and synthesized by the invention has the advantages of simple synthesis process, high yield and easy mass production.
Drawings
FIG. 1 is a scheme of the synthesis of the present invention:
a) the synthesis of the aryl azo pyrazole derivatives is carried out,
b) synthesis of aryl azo pyrazole polymer.
Fig. 2 is a nuclear magnetic hydrogen spectrum (deuterated chloroform) in the example:
a) nuclear magnetic hydrogen spectrum of aryl azo pyrazole derivative,
b) nuclear magnetic hydrogen spectrum of azo pyrazole polymer.
FIG. 3 is an infrared spectrum of the polyamidoamine, synthetic arylazopyrazole derivative and polymer of the examples.
Fig. 4 is an ultraviolet-visible absorption spectrum of the example:
a) purple light (405nm, 20 mW/cm)2) Irradiating the mixture to perform isomerization from a trans state to a cis state,
b) green light (520nm, 20 mW/cm)2) Cis-reversion to trans-reversion upon irradiation.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
1)4- (methylthio) aniline (2.78g, 20mmol) was dissolved in a mixed solution of concentrated hydrochloric acid (12M, 0.5mL) and 2mL ethanol and cooled to 0 ℃. 2mL of an aqueous solution of sodium nitrite (1.7g, 24mmol) was slowly added dropwise to the above solution and stirred for 1h to prepare the diazonium salt. Acetylacetone (2.6g, 26mmol) was added to a 50% ethanol aqueous solution followed by sodium acetate (4.92g, 60mmol) and cooling. The above diazonium salt solution was slowly added dropwise to the solution and the reaction was stirred, and the resulting yellow precipitate was filtered and washed with 200mL of 50% ethanol in water to give a yellow crude arylazoacetylacetone product. Arylazoacetylacetone (2.5g, 10mmol) was dissolved in 50mL of ethanol and then hydrazine hydrate (0.6g, 12mmol) was added dropwise thereto, and the mixed liquid was heated to 70 ℃ under stirring under a nitrogen atmosphere for 24 hours under reflux. After completion of the reaction, it was cooled to room temperature, the solvent was concentrated and dissolved in 50mL of dichloromethane, and washed 3 times with 200mL of saturated sodium chloride solution. The resulting organic layer was dried over 10g of anhydrous magnesium sulfate and concentrated to give arylazopyrazole, which was finally purified by column chromatography (ethyl acetate: petroleum ether ═ 1:1) to give the pure product.
2) Arylazo pyrazole (1.5g, 6mmol) was dissolved in 50mL acetonitrile, then 12-bromododecyl alcohol (2.05g, 8mmol), potassium carbonate (2.76g, 20mmol) and potassium iodide (1.32g, 8mmol) were added sequentially, and the mixture was heated to 68 ℃ under nitrogen atmosphere for reflux reaction for 24 h. After completion of the reaction, the inorganic salts were removed by filtration and the filtrate was concentrated to dryness under reduced pressure, then dissolved with 100mL of dichloromethane and washed with 300mL of saturated sodium chloride solution. The organic layer was dried over 10g of anhydrous sodium sulfate and concentrated to give an intermediate product, which was finally purified by column chromatography (ethyl acetate: n-hexane ═ 3:1) to give the desired compound. The resulting compound (1.3g, 3mmol) was dissolved in 50mL of anhydrous tetrahydrofuran and cooled to 0 deg.C, followed by the addition of triethylamine (0.91g, 9mmol), followed by the addition of a mixed solution of acryloyl chloride (0.81g, 9mmol) and 10mL of anhydrous tetrahydrofuran and continued stirring for 36 h. After the reaction was completed, the triethylamine salt was removed by filtration, concentrated to dryness and dissolved in 100mL of dichloromethane, and washed 4 times with 300mL of saturated sodium chloride solution to completely remove the triethylamine salt and acryloyl chloride. The organic phase is dried over 10g of anhydrous sodium sulfate and concentrated to dryness, and finally purified by column chromatography (ethyl acetate: petroleum ether ═ 1:2) to give the desired arylazopyrazole derivative.
3) The arylazopyrazole derivative (0.72G, 1.45mmol) was dissolved well in 10mL of methanol, and then a solution of polyamidoamine dendrimer (G3, 200mg, 0.029mmol) in methanol (5mL) was slowly added dropwise in an ice bath. In N2Heating the system to 50 ℃ in the atmosphere, and stirring for 24h at constant temperature. The reacted solution was concentrated and poured into 500mL of cold ether to precipitate the product and remove excess azobenzene acrylate. The filtered solid was dried under vacuum at 40 ℃ for 30h to give a dry arylazopyrazole polymer.
Example 2
1)4- (methylthio) aniline (1.36g, 10mmol) was dissolved in a mixed solution of concentrated hydrochloric acid (12M, 0.4mL) and 3mL of ethanol and cooled to 0 ℃. 1mL of an aqueous solution of sodium nitrite (1.2g, 17mmol) was slowly added dropwise to the above solution and stirred for 1.5h to prepare the diazonium salt. Acetylacetone (2g, 20mmol) was added to a 70% ethanol aqueous solution followed by sodium acetate (4g, 49mmol) and cooling. The above diazonium salt solution was slowly added dropwise to the solution and the reaction was stirred, and the resulting yellow precipitate was filtered and washed with 200mL of 70% ethanol in water to give a yellow crude arylazoacetylacetone product. Arylazoacetylacetone (1g, 4mmol) was dissolved in 20mL of ethanol and then hydrazine hydrate (0.5g, 10mmol) was added dropwise thereto, and the mixed liquid was heated to 80 ℃ under stirring under a nitrogen atmosphere and refluxed for 18 hours. After completion of the reaction, it was cooled to room temperature, the solvent was concentrated and dissolved in 30mL of dichloromethane, and extracted 2 times with 100mL of saturated sodium chloride solution. The resulting organic layer was dried over 10g of anhydrous magnesium sulfate and concentrated to give arylazopyrazole, which was finally purified by column chromatography (ethyl acetate: petroleum ether ═ 1:2) to give the pure product.
2) Arylazo pyrazole (0.8g, 3.3mmol) was dissolved in 30mL acetonitrile, then 12-bromododecyl alcohol (2g, 7.5mmol), potassium carbonate (2.5g, 18mmol) and potassium iodide (1.0g, 6mmol) were added sequentially, and the mixture was heated to 80 ℃ under nitrogen atmosphere and refluxed for 36 h. After completion of the reaction, the inorganic salts were removed by filtration and the filtrate was concentrated to dryness under reduced pressure, then dissolved with 80mL of dichloromethane and washed with 200mL of saturated sodium chloride solution. The organic layer was dried over 10g of anhydrous sodium sulfate and concentrated to give an intermediate product, which was finally purified by column chromatography (ethyl acetate: n-hexane ═ 3:2) to give the desired compound. The resulting compound (0.5g, 1.2mmol) was dissolved in 20mL of anhydrous tetrahydrofuran and cooled to 0 deg.C, followed by the addition of triethylamine (0.8g, 7.9mmol), followed by the addition of a mixed solution of acryloyl chloride (0.9g, 10mmol) and 20mL of anhydrous tetrahydrofuran and continued stirring for 36 h. After the reaction was completed, the triethylamine salt was removed by filtration, concentrated to dryness and dissolved in 80mL of dichloromethane, and washed 4 times with 200mL of saturated sodium chloride solution to completely remove the triethylamine salt and acryloyl chloride. The organic phase is dried over 10g of anhydrous sodium sulfate and concentrated to dryness, and finally purified by column chromatography (ethyl acetate: petroleum ether ═ 1:3) to give the desired arylazopyrazole derivative.
3) The arylazopyrazole derivative (1.4G, 2.88mmol) was dissolved well in 20mL of methanol and then a solution of polyamidoamine dendrimer (G3, 500mg, 0.072mmol) in methanol (20mL) was slowly added dropwise in an ice bath. In N2The temperature of the system is raised to 45 ℃ under the atmosphere, and the system is stirred for 48 hours at constant temperature. The reacted solution was concentrated and poured into 800mL of cold ether to precipitate the product and remove excess azobenzene acrylate. The filtered solid was dried under vacuum at 45 ℃ for 48h to give a dry arylazopyrazole polymer.
Example 3
1)4- (methylthio) aniline (5g, 36mmol) was dissolved in a mixed solution of concentrated hydrochloric acid (12M, 2mL) and 10mL of ethanol and cooled to 0 ℃.5mL of an aqueous solution of sodium nitrite (6.9g, 100mmol) was slowly added dropwise to the above solution and stirred for 2h to prepare the diazonium salt. Acetylacetone (10g, 100mmol) was added to an aqueous solution containing 80% ethanol followed by sodium acetate (10g, 122mmol) and cooling. The above diazonium salt solution was slowly added dropwise to the solution and the reaction was stirred, and the resulting yellow precipitate was filtered and washed with 300mL of an aqueous solution containing 80% ethanol to give a yellow crude arylazoacetylacetone product. Arylazaacetylacetone (4g, 16mmol) was dissolved in 60mL of ethanol and then hydrazine hydrate (4g, 80mmol) was added dropwise thereto, and the mixed liquid was heated to 80 ℃ under stirring under a nitrogen atmosphere under reflux for 48 hours. After completion of the reaction, it was cooled to room temperature, the solvent was concentrated and dissolved in 80mL of dichloromethane, and extracted 5 times with 400mL of saturated sodium chloride solution. The resulting organic layer was dried over 10g of anhydrous magnesium sulfate and concentrated to give arylazopyrazole, which was finally purified by column chromatography (ethyl acetate: petroleum ether ═ 1: 4) to give the pure product.
2) Arylazo pyrazole (3g, 12mmol) was dissolved in 50mL acetonitrile, then 12-bromododecyl alcohol (10g, 39mmol), potassium carbonate (10g, 72mmol) and potassium iodide (2.0g, 12mmol) were added sequentially, and the mixture was heated to 75 ℃ under nitrogen atmosphere and refluxed for 48 h. After completion of the reaction, the inorganic salts were removed by filtration and the filtrate was concentrated to dryness under reduced pressure, then dissolved with 100mL of dichloromethane and washed with 300mL of saturated sodium chloride solution. The organic layer was dried over 10g of anhydrous sodium sulfate and concentrated to give an intermediate product, which was finally purified by column chromatography (ethyl acetate: n-hexane ═ 1:1) to give the desired compound. The resulting compound (2g, 4.8mmol) was dissolved in 60mL of anhydrous tetrahydrofuran and cooled to 0 deg.C, followed by the addition of triethylamine (2g, 19.8mmol), followed by the addition of a mixed solution of acryloyl chloride (2g, 22mmol) and 30mL of anhydrous tetrahydrofuran and continued stirring for 48 h. After the reaction was completed, the triethylamine salt was removed by filtration, concentrated to dryness and dissolved in 30mL of dichloromethane, and washed 5 times with 200mL of a saturated sodium chloride solution to completely remove the triethylamine salt and acryloyl chloride. The organic phase is dried over 10g of anhydrous sodium sulfate and concentrated to dryness, and finally purified by column chromatography (ethyl acetate: petroleum ether ═ 3:2) to give the desired arylazopyrazole derivative.
3) Coupling aryl radicalsThe azapyrazole derivative (0.74G, 1.52mmol) was dissolved well in 15mL of methanol, and then a solution of polyamidoamine dendrimer (G3, 300mg, 0.043mmol) in methanol (15mL) was slowly added dropwise in an ice bath. In N2Heating the system to 50 ℃ in the atmosphere, and stirring for 48h at constant temperature. The reacted solution was concentrated and poured into 600mL of cold ether to precipitate the product and remove excess azobenzene acrylate. The filtered solid was dried under vacuum at 50 ℃ for 48h to give a dry arylazopyrazole polymer.
In conclusion, the invention provides a synthesis method of a visible-light-responsive aryl azo pyrazole polymer. The aryl azo pyrazole derivatives and polymers in example 1 of the present invention were confirmed by nuclear magnetic hydrogen spectroscopy (fig. 2). The chemical structure of the arylazopyrazole polymer in the examples of the invention was demonstrated by infrared spectroscopy (FIG. 3). Isomerization and reversion of arylazopyrazole polymers in the examples of the invention was demonstrated by uv-vis absorption spectroscopy (figure 4).
Claims (7)
1. A visible-light responsive arylazopyrazole polymer characterized by: the aryl azo pyrazole derivative is covalently grafted on the surface of the dendritic polymer through Michael addition reaction, and the structural formula of the obtained aryl azo pyrazole polymer is as follows:
2. the method of synthesizing a visible light-responsive arylazopyrazole polymer according to claim 1, which comprises the steps of:
the method comprises the following steps: preparation of arylazopyrazoles: dissolving 4- (methylthio) aniline in a mixed solution of concentrated hydrochloric acid and ethanol, and cooling to 0-5 ℃; slowly dripping sodium nitrite water solution into the solution and stirring for 1-2h to prepare diazonium salt; adding acetylacetone to a mixed solution of ethanol and water, then adding sodium acetate, and cooling to 0-5 deg.C; slowly dripping the diazonium salt solution into the solution and continuously stirring for reaction, filtering the obtained yellow precipitate and washing the yellow precipitate by using a mixed solution of ethanol and water to obtain a yellow crude product of aryl azo acetylacetone; dissolving aryl azo acetylacetone in ethanol, dropwise adding hydrazine hydrate into the ethanol, stirring and heating the mixed liquid to 60-80 ℃ under the nitrogen atmosphere, and carrying out reflux reaction for 12-48 h; after the reaction is finished, cooling to room temperature, concentrating the solvent, dissolving the solvent by using dichloromethane, and washing the solvent for multiple times by using a saturated sodium chloride solution; drying the obtained organic layer with anhydrous magnesium sulfate, concentrating to obtain aryl azo pyrazole, and finally performing column chromatography purification to obtain an expected product;
step two: preparation of arylazopyrazole derivatives: dissolving aryl azo pyrazole in acetonitrile, sequentially adding 12-bromododecyl alcohol, potassium carbonate and potassium iodide, heating the mixed solution to 60-70 ℃ in a nitrogen atmosphere, and carrying out reflux reaction for 24-48 h; after the reaction is finished, filtering to remove inorganic salt, concentrating the filtrate under reduced pressure until the filtrate is dried, dissolving the filtrate by using dichloromethane, and washing the dissolved filtrate by using a saturated sodium chloride solution; drying the organic layer by using anhydrous sodium sulfate, concentrating to obtain an intermediate product, and finally purifying by column chromatography to obtain a desired compound; dissolving the obtained compound in anhydrous tetrahydrofuran, cooling to 0-5 ℃, then adding triethylamine, then adding a mixed solution of acryloyl chloride and the anhydrous tetrahydrofuran, and continuing stirring for 24-36 h; after the reaction is finished, filtering to remove triethylamine salt, concentrating to be dry, dissolving with dichloromethane, and washing with a saturated sodium chloride solution for multiple times to completely remove the triethylamine salt and acryloyl chloride; drying the organic phase by using anhydrous sodium sulfate, concentrating to be dry, and finally purifying by using column chromatography to obtain the aryl azo pyrazole derivative;
step three: preparation of aryl azo pyrazole polymer: fully dissolving the aryl azo pyrazole derivative in methanol, and slowly dropwise adding a methanol solution of third-generation polyamide-amine dendritic macromolecules; after the dropwise addition is finished, placing the mixed solution in an oil bath at the temperature of 40-50 ℃ under the nitrogen atmosphere, and stirring for reaction for 24-36 h; pouring the reacted solution into a large amount of cold diethyl ether to precipitate out the product and remove the excess arylazopyrazole derivative; and drying the filtered product at 40-45 ℃ for 30-36h in vacuum to obtain the dried aryl azo pyrazole polymer.
3. The method of synthesizing a visible light responsive arylazopyrazole polymer according to claim 2, wherein: in the first step, the molar ratio of 4- (methylthio) aniline to sodium nitrite to acetylacetone to sodium acetate is 1:1:1:2 to 1:3:3: 5; the volume ratio of the concentrated hydrochloric acid to the ethanol in the mixed solution of the concentrated hydrochloric acid and the ethanol is 1: 2-1: 10; the volume ratio of ethanol to water in the mixed solution of ethanol and water is 1: 1-4: 1; the molar ratio of the aryl azo acetylacetone to the hydrazine hydrate is 1: 1-1: 6; the volume ratio of the dichloromethane to the saturated sodium chloride solution is 1: 2-1: 6.
4. The method of synthesizing a visible light responsive arylazopyrazole polymer according to claim 2, wherein: in the first step, the saturated sodium chloride solution is washed for 2-6 times; developing agents used for the column chromatography purification of the aryl azo pyrazole are ethyl acetate and petroleum ether, and the volume ratio of the developing agents to the petroleum ether is 1: 1-1: 5.
5. The method of synthesizing a visible light responsive arylazopyrazole polymer according to claim 2, wherein: in the second step, the molar ratio of the aryl azo pyrazole to the potassium iodide to the potassium carbonate to the 12-bromododecyl alcohol is 2:1:5: 3-2: 3:12: 9; the molar ratio of the intermediate product to the triethylamine to the acryloyl chloride is 1:3: 3-1: 8: 9.
6. The method of synthesizing a visible light responsive arylazopyrazole polymer according to claim 2, wherein: the volume ratio of the dichloromethane to the saturated sodium chloride solution in the second step is 1: 2-1: 8; in the second step, the saturated sodium chloride solution is washed for 2-5 times; developing agents used for intermediate product column chromatography purification are ethyl acetate and n-hexane, and the volume ratio of the developing agents to the n-hexane is 1: 1-3: 2; developing agents used for column chromatography purification of the aryl azo pyrazole derivative are ethyl acetate and petroleum ether, and the volume ratio of the developing agents is 1: 3-2: 1.
7. The method of synthesizing a visible light responsive arylazopyrazole polymer according to claim 2, wherein: in the third step, the molar ratio of the polyamide-amine (PAMAM) dendritic macromolecule to the aryl azo pyrazole derivative is 1: 30-1: 60; the volume ratio of the methanol to the ether is 1: 20-1: 40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110013945.7A CN112831057B (en) | 2021-01-06 | 2021-01-06 | Visible light response aryl azo pyrazole polymer and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110013945.7A CN112831057B (en) | 2021-01-06 | 2021-01-06 | Visible light response aryl azo pyrazole polymer and synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112831057A CN112831057A (en) | 2021-05-25 |
| CN112831057B true CN112831057B (en) | 2022-02-15 |
Family
ID=75926290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110013945.7A Active CN112831057B (en) | 2021-01-06 | 2021-01-06 | Visible light response aryl azo pyrazole polymer and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112831057B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432497A (en) * | 2011-09-23 | 2012-05-02 | 北京化工大学 | Synthesis and application of bis-o-substituted acrylate azobenzene containing intramolecular hydrogen bonds |
| CN109232428B (en) * | 2018-10-26 | 2022-02-15 | 上海交通大学 | Pyrazolyl azophenol compound and synthesis and derivation thereof |
| CN110437383B (en) * | 2019-07-16 | 2020-10-13 | 北京科技大学 | Preparation method of azo polymer for light-regulating solid-liquid conversion |
| CN111233698A (en) * | 2020-02-15 | 2020-06-05 | 桂林理工大学 | Polymerizable asymmetric azobenzene and preparation method thereof |
-
2021
- 2021-01-06 CN CN202110013945.7A patent/CN112831057B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112831057A (en) | 2021-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110437383B (en) | Preparation method of azo polymer for light-regulating solid-liquid conversion | |
| CN112778327B (en) | Organic non-fullerene electron acceptor material and preparation method and application thereof | |
| CN112300201B (en) | Synthesis and preparation method of trimeric indenyl coumarin-corrole-porphyrin quaternary system star-shaped compound | |
| CN109096313B (en) | Preparation method of trimeric indenyl corrole-porphyrin-fullerene star-shaped compound | |
| CN114773605B (en) | Preparation method of selenium-containing polymer taking carbamate bond as core | |
| CN108619995B (en) | Reversible optically-controlled fluorine-containing azo surfactant and preparation method thereof | |
| CN112831057B (en) | Visible light response aryl azo pyrazole polymer and synthesis method thereof | |
| CN112442054B (en) | Preparation method of trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound | |
| CN111004146A (en) | Liquid azophenyl molecular solar thermal fuel and synthesis method and application thereof | |
| CN109776329B (en) | Multi-component acrylate compound capable of photo-induced chiral turnover, preparation method and device | |
| CN111285982B (en) | Chiral supramolecular azobenzene assembly and in-situ construction method | |
| CN113024540B (en) | Preparation method and application of nonlinear compound with D-pi-A structure | |
| CN113234097B (en) | tBu-azaBODIPY photo-thermal dye and preparation method thereof | |
| CN113461564A (en) | 4, 4' -dihydroxy-diazobenzophenone and preparation method thereof | |
| CN108892969A (en) | 3,5- non-aryl replace R-azaBODIPY fluorescent dye and preparation method thereof | |
| CN111747865A (en) | Modified azobenzene compound and preparation method and application thereof | |
| CN109384909B (en) | Spinnable azobenzene polymer energy storage material and preparation method thereof | |
| CN107628966B (en) | Preparation method of three-arm chain transfer agent with photoresponse | |
| CN111233697A (en) | Acrylate azobenzene capable of solid-liquid conversion and preparation method thereof | |
| CN111961067A (en) | Azo-based dicarbole derivative and preparation method thereof | |
| CN113072561A (en) | Synthesis method of long-wavelength asymmetric rhodamine dye | |
| CN115850993B (en) | Chiral amphiphilic near-infrared aza-BODIPY dye and preparation method thereof | |
| CN111233698A (en) | Polymerizable asymmetric azobenzene and preparation method thereof | |
| CN114702500B (en) | Fluorescent material with pressure-induced color change property and application thereof in anti-counterfeiting | |
| CN113620977B (en) | Synthesis method of thiazolopyrimidinone acetic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |