CN111518297A - Preparation method of visible light stimulus responsive polyacrylamide supramolecular film - Google Patents
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Abstract
The invention discloses a preparation method of a polyacrylamide supramolecular film with visible light stimulus response, which comprises the steps of taking acrylamide, a tetra-o-methoxyazobenzene functionalized acrylamide monomer and beta-cyclodextrin functionalized acrylamide as reaction monomers, wrapping the tetra-o-methoxyazobenzene group by the beta-cyclodextrin to be taken as a physical crosslinking point, polymerizing under the initiation of an initiator 2,2' -aza-bis (2-imidazoline) dihydrochloride, and washing an obtained copolymer by acetone. The copolymer is swelled to form a film having visible light stimulus response and temperature response properties. The preparation method is simple, the raw materials are easy to obtain, and the obtained film has good stability and has visible light stimulation response and temperature response performances. The material has certain academic value and wide application prospect in the fields of optical information conversion and storage, intelligent response materials, sensors and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of a visible light stimulus responsive polyacrylamide supramolecular film.
Background
In recent years, stimulus responsiveness is a popular direction for researching intelligent materials, and at present, a common method is to connect and construct elements through non-covalent bond action so as to realize responsiveness of temperature, illumination, pH, solvent and the like. The stimuli-responsive polymer is used as a novel intelligent material, and has potential application prospects in the fields of shape memory materials, sensors, self-repairing materials, medicine carrying and the like.
Light is an excellent external stimulus with the advantage of spatial and temporal control. Tetramethoxyazobenzene is of interest because of its cis-trans isomerism under visible light irradiation, which has the advantage of less tissue damage and allows deeper penetration than ultraviolet light. Polyacrylamide is widely studied for its good salt resistance, shear resistance and oil repellency, and therefore, it is of great practical significance to develop novel materials with different properties and uses through chemical modification.
Disclosure of Invention
The invention aims to provide a preparation method of a visible light stimulus response polyacrylamide film with low cost and simple operation.
The specific technical scheme for realizing the purpose of the invention is as follows:
a preparation method of a polyacrylamide supramolecular film responding to visible light stimulation comprises the following specific steps:
step 1: synthesis of tetra-o-methoxyazobenzene functionalized acrylamide monomer
(1) Synthesis of 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene, i.e. Synthesis of Compound a
Mixing 2, 6-dimethoxyaniline and 5-15% hydrochloric acid, quickly adding a sodium nitrite aqueous solution into the 2, 6-dimethoxyaniline solution under ice bath, dropwise adding an aqueous solution of 3, 5-dimethoxyaniline and sodium hydroxide after 10-30 minutes, reacting for 3 days, acidifying until the pH value is 5-6, stirring for 3-6 hours, and cooling with ice water; filtering and washing the precipitate by ice water to obtain a red solid, namely 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene; wherein the molar ratio of the 2, 6-dimethoxyaniline to the hydrochloric acid is 1: 0.8-1.5; the molar ratio of the 2, 6-dimethoxyaniline to the sodium nitrite to the 3, 5-dimethoxyaniline is 1: 0.8-1.2; the molar ratio of the 3, 5-dimethoxyaniline to the sodium hydroxide is 1: 1.1-5;
(2) synthesis of 4- (acrylamide) benzoic acid Compound b
Adding 4-aminobenzoic acid into a reaction bottle, adding N, N-dimethylformamide and pyridine serving as solvents, and cooling the solution to 0-5 ℃; adding acryloyl chloride into the solution, and stirring for reaction for 2-5 hours; pouring the mixture into water, filtering, washing a filter cake with water and diethyl ether, and obtaining a white solid, namely 4- (acrylamide) benzoic acid; wherein the molar ratio of the 4-aminobenzoic acid to the acryloyl chloride is 1: 1-2;
(3) synthesis of tetra-o-methoxyazobenzene functionalized acrylamide monomer, namely compound c
Adding 4- (acrylamide) benzoic acid, 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene and an anhydrous solvent N, N-dimethylformamide into a reaction container under the atmosphere of nitrogen, and stirring for dissolving; adding 4-dimethylaminopyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in ice bath, and reacting at normal temperature for 12-30 hours; distilling under reduced pressure to remove the solvent, and separating by column chromatography to obtain a red solid, namely the tetrao-methoxy azobenzene functionalized acrylamide monomer; wherein the molar ratio of the 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene to the 4- (acrylamide) benzoic acid to the 4-dimethylaminopyridine is 1: 1.0-1.2: 0.02-0.1; the molar ratio of 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene to 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 1: 1-3;
step 2: synthesis of 6-amino-beta-cyclodextrin
(1) Synthesis of 6-p-toluenesulphonic acid-beta-cyclodextrin compound d
Suspending beta-cyclodextrin in water under mechanical stirring, dropwise adding a sodium hydroxide aqueous solution cooled to room temperature, stirring for 0.5-2 hours, dropwise adding an acetonitrile solution of p-toluenesulfonyl chloride into the solution at a speed of 1-3 seconds per drop by using a constant pressure funnel, and continuously stirring for 2-4 hours after the dropwise adding is finished; adjusting the pH value of the filtrate obtained by filtering to 7-8 by using 0.5-3 mol/L hydrochloric acid, refrigerating at 0-5 ℃ for 10-15 hours, filtering, and recrystallizing a filter cake by using water to obtain a white solid, namely 6-p-toluenesulfonic acid-beta-cyclodextrin; wherein the molar ratio of the beta-cyclodextrin to the sodium hydroxide to the p-methylbenzenesulfonyl chloride is 1: 2-4: 0.8-1.5;
(2) synthesis of 6-amino-beta-cyclodextrin, Compound e
Adding 6-p-toluenesulfonic acid-beta-cyclodextrin and ammonia water into a reaction bottle, and heating and refluxing for reaction at 50-65 ℃ for 3-5 days; dropping the reaction solution into acetone for precipitation, filtering, dissolving a filter cake by using a mixed solution of water and methanol with the ratio of 2-4: 1, dropping the solution into the acetone again for precipitation, and filtering to obtain a white solid, namely 6-amino-beta-cyclodextrin;
(3) synthesis of beta-cyclodextrin functionalized acrylamide, i.e. compound f
Dissolving 6-amino-beta-cyclodextrin in an aqueous solution of sodium bicarbonate, and adjusting the pH of the solution to 8-10 by using a sodium hydroxide solid; adding acryloyl chloride into the solution at the temperature of 0-5 ℃, and stirring for reaction for 2-5 hours; then, evaporating the solution to 10-40% of the total volume, and dripping the solution into acetone for precipitation; collecting precipitate by centrifugation, drying the solid, dissolving the solid in a mixed solution of N, N-dimethylformamide and methanol in a ratio of 1: 0.8-2, centrifuging, dripping the obtained supernatant into acetone for precipitation, centrifuging, and washing the product with acetone to obtain beta-cyclodextrin functionalized acrylamide; wherein the molar ratio of the 6-amino-beta-cyclodextrin to the sodium bicarbonate to the acryloyl chloride is 1: 10-15: 1-3;
and step 3: synthesis of polyacrylamide supramolecular hydrogel responding to visible light stimulation
Mixing beta-cyclodextrin functionalized acrylamide and tetra-o-methoxyazobenzene functionalized acrylamide monomers in water, and stirring for 0.5-12 hours at normal temperature in the dark; adding acrylamide and a reaction initiator 2,2' -azabicyclo (2-imidazoline) dihydrochloride, and stirring for 2-10 hours at the temperature of 30-50 ℃ to obtain red hydrogel; washing with acetone to obtain the visible light stimulated response polyacrylamide supramolecular hydrogel; wherein the molar ratio of the tetrao-methoxyazobenzene functionalized acrylamide monomer to the beta-cyclodextrin functionalized acrylamide is 1: 0.8-1.5; the molar ratio of the tetrao-methoxyazobenzene functionalized acrylamide monomer to the acrylamide is 1: 100-200; the molar ratio of the tetrao-methoxy azobenzene functionalized acrylamide monomer to 2,2' -azabicyclo (2-imidazoline) dihydrochloride is 1: 0.5-2; wherein m represents the amount of a tetra-o-methoxyazobenzene functionalized acrylamide monomer, n represents the amount of beta-cyclodextrin functionalized acrylamide, l represents the amount of acrylamide, and m: n: l is 1:1: 100-500;
and 4, step 4: preparation of visible light stimulus responsive polyacrylamide supramolecular film
And (3) placing the hydrogel obtained in the step (3) in water, fully stirring and uniformly swelling at the temperature of 45-70 ℃ to prepare a 5-30% gel solution, cooling to room temperature, dripping the gel solution on a clean glass sheet, and naturally volatilizing water to obtain the visible light stimulus response polyacrylamide supramolecular film.
The tetrao-methoxy azobenzene functionalized acrylamide monomer contains a visible light response group, and the structure of the tetrao-methoxy azobenzene functionalized acrylamide monomer is shown as the following formula A:
the structure of the visible light stimulus responsive polyacrylamide hydrogel is shown as the following formula B:
wherein m represents the amount of the tetrao-methoxy azobenzene functionalized acrylamide monomer, n represents the amount of the beta-cyclodextrin functionalized acrylamide, l represents the amount of the acrylamide, and m: n: l is 1:1: 100-500.
The visible light stimulus response polyacrylamide supramolecular film prepared by the method contains tetra-o-methoxyazobenzene, photochemical reaction is carried out under the illumination of 520nm and 470nm, isomerization of tetra-o-methoxyazobenzene groups from trans to cis is carried out under the illumination of 520nm, and the tetra-o-methoxyazobenzene groups can be reversibly returned to the trans structure under the illumination of 470 nm.
The polyacrylamide supramolecular film has visible light stimulus response and temperature response performances, and can be reversely bent when a finger approaches; obviously curling the film on a heating table at the temperature of 30-45 ℃; and the film deformed after a period of 520nm illumination.
The invention has the advantages of
The invention can prepare film. The preparation method is simple, the raw materials are easy to obtain, and the obtained film has good stability and has visible light stimulation response and temperature response performances. The material has certain academic value and wide application prospect in the fields of optical information conversion and storage, intelligent response materials, sensors and the like.
Drawings
FIG. 1 shows a tetrakismethoxyazobenzene functionalized acrylamide monomer in example 1 of the present invention1H NMR chart;
FIG. 2 is a photograph of a gel in example 1 of the present invention;
FIG. 3 is a UV-VIS spectrum before and after UV irradiation of the polyacrylamide supramolecular film responding to the stimulation of visible light in example 3 of the invention;
FIG. 4 is an infrared analysis spectrum of a polyacrylamide film responding to a visible light stimulus in example 4 of the present invention;
FIG. 5 is a photograph showing the bending response of a visible light stimulus-responsive polyacrylamide film when a finger is in close proximity in example 5 of the present invention;
FIG. 6 is a photograph showing the response of a visible light stimulus-responsive polyacrylamide film in example 6 of the present invention on a 20-45 ℃ heating stage;
FIG. 7 is a photograph showing the response of the polyacrylamide film responding to visible light stimulus in example 7 of the present invention at 520nm in green light.
Detailed Description
The invention is described in detail below with reference to the accompanying drawings and examples.
Example 1
(a) In a 250ml single-neck flask, 2, 6-dimethoxyaniline (2.0g,13.0mmol) and hydrochloric acid (5.3ml, 10%) were mixed, and a solution of sodium nitrite (0.9g,13.0mmol) in water (13.3ml) was rapidly added to the 2, 6-dimethoxyaniline solution under ice-cooling, and after 10 minutes, a solution of 3, 5-dimethoxyphenol (2.1g,13.0mmol) and sodium hydroxide (1.0g,24.7mmol) in water (133.0ml) was added dropwise; the reaction mixture was stirred for 3 days and then acidified to pH 6, stirred for 3 hours and cooled with ice water. Filtering, washing the precipitate with ice water, and drying in a vacuum oven; column chromatography of the solid (dichloromethane: methanol: 60:1) gave 1.85g of a red solid.
(b) 4-Aminobenzoic acid (1.4g,10.0mmol) was added to a reaction flask, and the solvents N, N-dimethylformamide (10.0ml) and pyridine (0.5ml) were added to form a solution and cooled to 0 ℃; acryloyl chloride (0.9g,10.0mmol) was added to the above solution and the resulting mixture was stirred for 3 hours; thereafter, the reaction mixture was poured into 200ml of water, and the white solid obtained by filtration was washed with water and ether and dried under vacuum to obtain 1.8g of a product.
(c) Adding 4- (acrylamide) benzoic acid (300.0mg,1,57mmol) and 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene (500.0mg,1.57mmol) into a 100ml three-neck flask, adding 20ml of anhydrous N, N-dimethylformamide under nitrogen atmosphere, stirring for dissolving, adding 4-dimethylaminopyridine (5.8mg,0.05mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (362.0mg,1.88mmol) into ice bath, introducing nitrogen for 5min, removing the ice bath after 20min, stirring for reacting for 24 h at normal temperature, distilling under reduced pressure to remove the solvent, and performing column chromatography on the obtained solid (dichloromethane: methanol ═ 60:1) to obtain 0.30g of red solid (tetrao-methoxy-azobenzene) which is 0.30g of red solidAzobenzene functionalized acrylamide monomer, process for producing the same, and use thereof1The H NMR spectrum is shown in figure 1 (where represents the dimethylsulfoxide-d 6 solvent peak).
(d) Beta-cyclodextrin (112.0g,98.7mmol) and 0.8L of water are added into a 2L four-neck flask, white suspension is obtained by mechanical stirring, sodium hydroxide (10.7g,266.7mmol) solution cooled to room temperature (32ml) is added into the solution dropwise, after 1 hour of continuous stirring, acetonitrile (48ml) solution of p-methylbenzenesulfonyl chloride (19.4g,101.9mmol) is added dropwise at the speed of 2 seconds/drop by using a constant pressure funnel, after the dropwise addition is finished, the stirring is continued for 3 hours, then the filtration is carried out, the pH of the filtrate is adjusted to 7 by using 1mol/L hydrochloric acid, the filtrate is refrigerated for 12 hours at the temperature of 0 ℃, the filtration is carried out, and the filter cake is recrystallized by using water to obtain 24.5g of white solid, namely 6-p-methylbenzenesulfonic acid-beta-cyclodextrin.
(e) Adding 6-p-toluenesulfonic acid-beta-cyclodextrin (4.2g,3.2mmol) and 150ml of ammonia water into a 250ml round-bottom flask, and heating and refluxing at 55 ℃ for 5 days; dropping the reaction liquid into 400ml of acetone to separate out a white solid, filtering, dissolving a filter cake by using a mixed solution of water and methanol in a ratio of 3:1, dropping the solution into 400ml of acetone to precipitate, and drying the filter cake obtained by filtering in a drying oven to obtain 1.6g of a product, namely 6-amino-beta-cyclodextrin.
(f) Adding 6-amino-beta-cyclodextrin (1.5g,1.3mmol) and sodium bicarbonate (1.5g,17.9mmol) in water (100ml) into a single-neck flask, adding a small amount of sodium hydroxide solid to adjust the pH of the solution to be approximately equal to 10, fully stirring until the solution is dissolved, adding acryloyl chloride under the ice bath condition, and continuously stirring for reacting for 4 hours; the solution is evaporated until about 15ml of solution is left, and the solution is dripped into 100ml of acetone to precipitate white solid, and the white solid is collected centrifugally; after drying the solid, the solid was washed with N, N-dimethylformamide: and (3) dissolving the mixed solution of methanol 1:1, dropping the supernatant obtained by centrifugation into 100ml of acetone for precipitation, washing the centrifugally collected solid twice by using acetone, and drying in a drying oven to obtain 1g of white solid, namely the beta-cyclodextrin functionalized acrylamide.
(g) Placing beta-cyclodextrin functionalized acrylamide (11.9mg,0.01mmol) and tetra-o-methoxyazobenzene functionalized acrylamide monomer (4.9mg,0.01mmol) in 1mL of distilled water, mixing, stirring overnight at normal temperature and in the dark to obtain a red turbid solution, adding main monomer acrylamide (140.0mg,1.98mmol) and a free radical initiator azobisisobutyrimidazoline hydrochloride (VA-044,3.0mg,0.01mmol), and heating and stirring for 8 hours at 50 ℃ for polymerization reaction; the hydrogel was washed with acetone to remove unreacted monomers, and a visible light stimulus-responsive polyacrylamide supramolecular hydrogel was prepared, and the photograph thereof is shown in fig. 2.
Example 2
And (2) putting the hydrogel obtained in the example 1 into water, fully stirring and uniformly swelling at 60 ℃ to prepare a 5% gel solution, cooling to room temperature, dripping the gel solution on a clean glass sheet, and naturally volatilizing the water to obtain the visible light stimulus response polyacrylamide supramolecular film.
Example 3
The film obtained in example 2 was monitored for changes in the photosensitive groups at different times under 520nm illumination using UV-visible absorption spectroscopy.
Referring to FIG. 3, it can be seen that under 520nm UV light, the absorption peak at 350nm on the UV-visible absorption spectrum decreases and the absorption peak at 420nm increases with increasing time, indicating that the tetrao-methoxyazobenzene isomerizes from trans to cis at 520nm, and the transition reaches equilibrium after one hour. The initial state can be recovered in about 1 minute under 470nm illumination.
Example 4
Referring to FIG. 4, a small piece of the film obtained in example 2 was subjected to IR spectrum characterization. The infrared spectrum of the obtained supramolecular polymer is 1028cm-1And 936cm-1The two sets of peaks, corresponding to the stretching vibration of ═ C-O-C of tetrao-methoxyazobenzene and the C-H bending vibration of the benzene ring, respectively, indicate the successful introduction of guest monomer.
Example 5
The polymer film obtained in example 2 was cut into a rectangular shape, gently gripped with tweezers, and slowly approached with a finger, and the response of the film to human body temperature was observed.
Referring to fig. 5, it can be seen from the film photograph that the film can be bent significantly in the direction opposite to the finger approach direction.
Example 6
The polymer film obtained in example 2 was placed on heating stages at 20, 25, 30, 35, 40, and 45 ℃ respectively to further illustrate the temperature response properties of the film.
Referring to fig. 6, the upper row of the film pictures before heating and the lower row of the film pictures after heating at corresponding temperatures are shown, and it can be seen from the film picture that the film edges are obviously bent on the heating tables at 30, 35, 40 and 45 ℃, which shows that the film has response to temperature, the film does not change when the temperature is lower than 30 ℃, and the film deforms when the temperature is higher than 30 ℃ under the stimulation of a heat source.
Example 7
The polymer film obtained in example 2 was placed on a flat table while being bent and irradiated with a strong torch having a filter cover of 520nm for 48min, to briefly explain the responsiveness of the film to visible light stimuli.
Referring to fig. 7, it can be seen from the film photograph that the degree of bending of the film is significantly reduced after the green light of 520nm is irradiated for 48min, indicating that the film has responsiveness to the green light of 520 nm.
Claims (5)
1. A preparation method of a polyacrylamide supramolecular film responding to visible light stimulation is characterized by comprising the following specific steps:
step 1: synthesis of tetra-o-methoxyazobenzene functionalized acrylamide monomer
(1) Synthesis of 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene, i.e. Synthesis of Compound a
Mixing 2, 6-dimethoxyaniline and 5-15% hydrochloric acid, quickly adding a sodium nitrite aqueous solution into the 2, 6-dimethoxyaniline solution under ice bath, dropwise adding an aqueous solution of 3, 5-dimethoxyaniline and sodium hydroxide after 10-30 minutes, reacting for 3 days, acidifying until the pH value is 5-6, stirring for 3-6 hours, and cooling with ice water; filtering and washing the precipitate by ice water to obtain a red solid, namely 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene; wherein the molar ratio of the 2, 6-dimethoxyaniline to the hydrochloric acid is 1: 0.8-1.5; the molar ratio of the 2, 6-dimethoxyaniline to the sodium nitrite to the 3, 5-dimethoxyaniline is 1: 0.8-1.2; the molar ratio of the 3, 5-dimethoxyaniline to the sodium hydroxide is 1: 1.1-5;
(2) synthesis of 4- (acrylamide) benzoic acid Compound b
Adding 4-aminobenzoic acid into a reaction bottle, adding N, N-dimethylformamide and pyridine serving as solvents, and cooling the solution to 0-5 ℃; adding acryloyl chloride into the solution, and stirring for reaction for 2-5 hours; pouring the mixture into water, filtering, washing a filter cake with water and diethyl ether, and obtaining a white solid, namely 4- (acrylamide) benzoic acid; wherein the molar ratio of the 4-aminobenzoic acid to the acryloyl chloride is 1: 1-2;
(3) synthesis of tetra-o-methoxyazobenzene functionalized acrylamide monomer, namely compound c
Adding 4- (acrylamide) benzoic acid, 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene and an anhydrous solvent N, N-dimethylformamide into a reaction container under the atmosphere of nitrogen, and stirring for dissolving; adding 4-dimethylaminopyridine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in ice bath, and reacting at normal temperature for 12-30 hours; distilling under reduced pressure to remove the solvent, and separating by column chromatography to obtain a red solid, namely the tetrao-methoxy azobenzene functionalized acrylamide monomer; wherein the molar ratio of the 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene to the 4- (acrylamide) benzoic acid to the 4-dimethylaminopyridine is 1: 1.0-1.2: 0.02-0.1; the molar ratio of 2,6, 2', 6' -tetramethoxy- (4-hydroxy) azobenzene to 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 1: 1-3;
step 2: synthesis of beta-cyclodextrin functionalized acrylamide
(1) Synthesis of 6-p-toluenesulphonic acid-beta-cyclodextrin compound d
Suspending beta-cyclodextrin in water under mechanical stirring, dropwise adding a sodium hydroxide aqueous solution cooled to room temperature, stirring for 0.5-2 hours, dropwise adding an acetonitrile solution of p-toluenesulfonyl chloride into the solution at a speed of 1-3 seconds per drop by using a constant pressure funnel, and continuously stirring for 2-4 hours after the dropwise adding is finished; adjusting the pH value of the filtrate obtained by filtering to 7-8 by using 0.5-3 mol/L hydrochloric acid, refrigerating at 0-5 ℃ for 10-15 hours, filtering, and recrystallizing a filter cake by using water to obtain a white solid, namely 6-p-toluenesulfonic acid-beta-cyclodextrin; wherein the molar ratio of the beta-cyclodextrin to the sodium hydroxide to the p-methylbenzenesulfonyl chloride is 1: 2-4: 0.8-1.5;
(2) synthesis of 6-amino-beta-cyclodextrin, Compound e
Adding 6-p-toluenesulfonic acid-beta-cyclodextrin and ammonia water into a reaction bottle, and heating and refluxing for reaction at 50-65 ℃ for 3-5 days; dropping the reaction solution into acetone for precipitation, filtering, dissolving a filter cake by using a mixed solution of water and methanol with the ratio of 2-4: 1, dropping the solution into the acetone again for precipitation, and filtering to obtain a white solid, namely 6-amino-beta-cyclodextrin;
(3) synthesis of beta-cyclodextrin functionalized acrylamide, i.e. compound f
Dissolving 6-amino-beta-cyclodextrin in an aqueous solution of sodium bicarbonate, and adjusting the pH of the solution to 8-10 by using a sodium hydroxide solid; adding acryloyl chloride into the solution at the temperature of 0-5 ℃, and stirring for reaction for 2-5 hours; then, evaporating the solution to 10-40% of the total volume, dropwise adding the solution into acetone for precipitation, collecting the precipitate through centrifugation, drying the solid, dissolving the solid in a mixed solution of N, N-dimethylformamide and methanol in a ratio of 1: 0.8-2, centrifuging, dropwise adding the obtained supernatant into acetone for precipitation, centrifuging, and washing the product with acetone to obtain the beta-cyclodextrin functionalized acrylamide; wherein the molar ratio of the 6-amino-beta-cyclodextrin to the sodium bicarbonate to the acryloyl chloride is 1: 10-15: 1-3;
and step 3: synthesis of polyacrylamide supramolecular hydrogel responding to visible light stimulation
Mixing beta-cyclodextrin functionalized acrylamide and tetra-o-methoxyazobenzene functionalized acrylamide monomers in water, and stirring for 0.5-12 hours at normal temperature in the dark; adding acrylamide and a reaction initiator 2,2' -azabicyclo (2-imidazoline) dihydrochloride, and stirring for 2-10 hours at the temperature of 30-50 ℃ to obtain red hydrogel; washing with acetone to obtain the visible light stimulated response polyacrylamide supramolecular hydrogel; wherein the molar ratio of the tetrao-methoxyazobenzene functionalized acrylamide monomer to the beta-cyclodextrin functionalized acrylamide is 1: 0.8-1.5; the molar ratio of the tetrao-methoxyazobenzene functionalized acrylamide monomer to the acrylamide is 1: 100-200; the molar ratio of the tetrao-methoxy azobenzene functionalized acrylamide monomer to 2,2' -azabicyclo (2-imidazoline) dihydrochloride is 1: 0.5-2; wherein m represents the amount of a tetra-o-methoxyazobenzene functionalized acrylamide monomer, n represents the amount of beta-cyclodextrin functionalized acrylamide, l represents the amount of acrylamide, and m: n: l is 1:1: 100-500;
and 4, step 4: preparation of visible light stimulus responsive polyacrylamide supramolecular film
And (3) placing the hydrogel obtained in the step (3) in water, fully stirring and uniformly swelling at the temperature of 45-70 ℃ to prepare a 5-30% gel solution, cooling to room temperature, dripping the gel solution on a clean glass sheet, and naturally volatilizing water to obtain the visible light stimulus response polyacrylamide supramolecular film.
2. The method according to claim 1, wherein the tetrakismethoxyazobenzene functionalized acrylamide monomer contains a visible light-responsive group having the following structure formula A:
3. a visible light stimulus responsive polyacrylamide supramolecular film prepared by the method of claim 1.
4. The visible light stimulus responsive polyacrylamide supramolecular membrane as claimed in claim 3, wherein the membrane comprises tetrakismethoxyazobenzene, wherein the photochemical reaction is carried out under 520nm and 470nm illumination, the tetrakismethoxyazobenzene group isomerizes from trans to cis under 520nm illumination, and the tetrakismethoxyazobenzene group reversibly returns to trans structure under 470nm illumination.
5. The visible light stimulus-responsive polyacrylamide supramolecular membrane as claimed in claim 3, wherein the polyacrylamide supramolecular membrane has visible light stimulus-responsive and temperature-responsive properties, and can be bent in the reverse direction when a finger approaches; obviously curling the film on a heating table at the temperature of 30-45 ℃; and the film deformed after a period of 520nm illumination.
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| CN115260690A (en) * | 2022-07-28 | 2022-11-01 | 复旦大学 | Visible light response supramolecular hydrogel and preparation method and application thereof |
| CN115403797A (en) * | 2022-08-30 | 2022-11-29 | 华东师范大学 | Slip ring supermolecule gel film with quick photoresponse performance and preparation method thereof |
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| CN112138636A (en) * | 2020-08-19 | 2020-12-29 | 江苏大学 | Environment-friendly intelligent adsorption material and preparation method and application thereof |
| CN112138636B (en) * | 2020-08-19 | 2023-04-07 | 江苏大学 | Environment-friendly intelligent adsorption material and preparation method and application thereof |
| CN115094450A (en) * | 2022-07-02 | 2022-09-23 | 重庆工商大学 | Synthetic method of organic polymeric flocculant |
| CN115260690A (en) * | 2022-07-28 | 2022-11-01 | 复旦大学 | Visible light response supramolecular hydrogel and preparation method and application thereof |
| CN115260690B (en) * | 2022-07-28 | 2023-05-30 | 复旦大学 | Super-molecular hydrogel with visible light response and preparation method and application thereof |
| CN115403797A (en) * | 2022-08-30 | 2022-11-29 | 华东师范大学 | Slip ring supermolecule gel film with quick photoresponse performance and preparation method thereof |
| CN115403797B (en) * | 2022-08-30 | 2023-07-25 | 华东师范大学 | Slip ring supermolecule gel film with rapid light response performance and preparation method thereof |
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