CN108948716B - Light-driven self-repairing supramolecular thin film based on multiple hydrogen bonds and preparation method thereof - Google Patents

Light-driven self-repairing supramolecular thin film based on multiple hydrogen bonds and preparation method thereof Download PDF

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CN108948716B
CN108948716B CN201710386004.1A CN201710386004A CN108948716B CN 108948716 B CN108948716 B CN 108948716B CN 201710386004 A CN201710386004 A CN 201710386004A CN 108948716 B CN108948716 B CN 108948716B
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polyacrylic acid
pyrimidone
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冯奕钰
司倩宇
封伟
杨伟翔
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Abstract

The invention discloses a light-driven self-repairing supramolecular film based on multiple hydrogen bonds and a preparation method thereof, wherein 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group reacts with polyacrylic acid to obtain polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidone, the polyacrylic acid is mixed with tetracarboxylazobenzene and then is subjected to suction filtration, and the filtrate after the suction filtration is used for forming a film. According to the invention, tetracarboxylazobenzene is introduced into a polyacrylic acid polymer to realize the optical drive of the film, and simultaneously, the self-repairing characteristic is introduced, and the self-repairing under the optical drive is realized by utilizing quadruple hydrogen bonds formed between 2-ureido-4 [ 1H ] -pyrimidone and hydrogen bonds formed between the tetracarboxylazobenzene to form supermolecule self-assembly.

Description

Light-driven self-repairing supramolecular thin film based on multiple hydrogen bonds and preparation method thereof
Technical Field
The invention belongs to the field of self-repair of materials, and particularly relates to a method for realizing self-repair of a film in a dynamic photoresponse process by utilizing ultraviolet light initiation.
Background
The device made of the polymer material with the light-induced deformation can be used in the aspects of intelligent sensors, engines, brakes, high-frequency oscillators, artificial cilia and the like. When azobenzene exists in the liquid crystal elastomer as chromophore, after being irradiated by ultraviolet light, the azobenzene can generate cis-trans isomeric change and convert a small amount of light energy into macroscopic mechanical motion, so that the bending-straightening, contraction-expansion change of the polymer is realized. The liquid crystal polymer is usually prepared by covalent bond crosslinking, but the preparation method is complicated and cannot obtain a good chemical structure.
The use of non-covalent bonds as cross-linking points for the preparation of the network polymer is simple and readily available. There are many non-covalent bonds, among which hydrogen bonds have a simple chemical structure, dynamic reversibility, and bond energy (2-20Kcal/mol) lower than that of covalent bonds (35-135Kcal/mol), so that they can be used to prepare functional materials such as self-healing materials. Moreover, the hydrogen bonds have directionality and attraction, and good mechanical strength can be obtained. Wherein, the 2-ureido-4 [ 1H ] -pyrimidone can form reversible quadruple hydrogen bonds and shows good temperature mechanical dependence. The rapid self-repairing solid material has the advantages of single composition by using a multiple hydrogen bond system, and the initiation of self-repairing does not need additional stimulation, such as a repairing agent, a plasticizer and a solvent, so that the performance of the material is not influenced by the self-repairing process. And local self-repairing can be realized by controlling the light switch. When ultraviolet light irradiates, the 2-ureido-4 [ 1H ] -pyrimidone is activated, absorbs light and converts the light into heat, so that the arrangement of hydrogen bonds becomes disordered, the molecular weight and the viscosity of the supramolecular polymer material are reduced, and the introduced damage is repaired. Meanwhile, azobenzene absorbs ultraviolet light, changes from trans-form to cis-form, shortens the molecular length, and drives the polymer film to bend, thereby realizing the purpose of converting a small amount of light into macroscopic mechanical motion. Finally, the repair of the film in the bending process is realized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a light-driven self-repairing supramolecular film based on multiple hydrogen bonds and a preparation method thereof, wherein the quadruple hydrogen bonds are used for self-repairing, the repairing time is short, the efficiency is high, and the film can be repeatedly repaired, so that the self-repairing of the film in the response process is realized, and the service life of the material is prolonged; the method realizes self-repair of the supermolecule polymer film in the dynamic photoresponse process, and is simple in preparation method and high in repair efficiency.
The technical purpose of the invention is realized by the following technical scheme:
the light-driven self-repairing supramolecular film based on multiple hydrogen bonds is composed of polyacrylic acid and tetracarboxylazobenzene, wherein the polyacrylic acid is modified based on pyrimidone, the main chain of the polyacrylic acid is a main chain connected with carbon and carbon, partial side chains are carboxyl, and partial side chains are 2-ureido-4 [1 ] hydrogen-pyrimidone connected with the main chain through carbonyl.
The mass ratio (molar ratio) of polyacrylic acid to tetracarboxylazobenzene is (15-55): 1, preferably (20-40): 1.
the polyacrylic acid has a number average molecular weight of 400000 to 800000, preferably 500000 to 600000.
The preparation method of the film comprises the following steps:
dispersing tetracarboxylazobenzene and polyacrylic acid based on pyrimidone modification respectively in an organic solvent, dripping an organic solution of polyacrylic acid based on pyrimidone modification into the organic solution of tetracarboxylazobenzene, continuously stirring and dispersing, performing suction filtration to obtain a filtrate, and uniformly spreading the filtrate on a substrate to dry to obtain the film.
The ratio of the amounts of substances based on pyrimidone-modified polyacrylic acid and tetracarboxylazobenzene (molar ratio) is (15-55): 1, preferably (20-40): 1.
the organic solvent for dispersing the pyrimidone-modified polyacrylic acid is the same as the organic solvent for dispersing the tetracarboxylic azobenzene, and is, for example, N, N '-dimethylformamide, N, N' -dimethylacetamide, or N-methylpyrrolidone.
Suspending, steaming and concentrating the filtrate, dripping the concentrated filtrate on a quartz plate, and fully paving; putting the mixture into a vacuum oven at the normal temperature of 20-25 ℃ for 20-24 h; and then putting the film into a vacuum oven at 50-60 ℃ for drying for 20-24 h to finally obtain the film.
The organic solution based on the pyrimidone modified polyacrylic acid is dripped into the organic solution of the tetra-carboxyl azobenzene at the dripping speed of 1-3 ml per minute and is continuously stirred and dispersed for 10-12 hours.
The tetracarboxylic azobenzene used was prepared according to the following procedure: dissolving p-amino isophthalic acid in an aqueous solution of sodium hydroxide, and adding sodium nitrite; slowly dropwise adding the solution into a hydrochloric acid solution, and stirring at 0 ℃ to obtain diazonium salt; dissolving isophthalic acid into an aqueous sodium hydroxide solution; keeping the temperature at 0 ℃, slowly adding the diazonium salt into the isophthalic acid solution, and keeping the pH alkaline; stirring for 8-10 hours, and adjusting the pH value to 3 by hydrochloric acid to generate a large amount of precipitates; performing suction filtration, adding a large amount of water, performing suction filtration, and drying; dissolving the product in a mixed solution of ethanol and water, heating to ensure supersaturation, performing rapid suction filtration, freezing for precipitation, and performing suction filtration; putting the product into a vacuum oven for drying to obtain tetracarboxylazobenzene; the ratio of the amounts of the p-aminoisophthalic acid and the sodium nitrite species is 1: (1-1.5).
Specifically, 15mmol of p-aminoisophthalic acid was dissolved in 40ml of a 1mol/L aqueous solution of sodium hydroxide, and ammonium nitrite was added in an amount 1 to 1.5 times as much as that of p-aminoisophthalic acid; slowly dripping the solution into 90ml of hydrochloric acid solution (1M), and stirring for 30min at 0 ℃ to obtain diazonium salt; dissolving 15mmol of isophthalic acid into 30ml of 1mol/L sodium hydroxide aqueous solution; keeping the temperature at 0 ℃, slowly adding the obtained diazonium salt into the isophthalic acid alkali solution, and keeping the PH at 9; stirring for 8-10 hours, and adjusting the pH value to 3 by using a hydrochloric acid solution (1M) to generate a large amount of precipitates; performing suction filtration, adding a large amount of water, performing suction filtration, and drying; dissolving the product in a mixed solution of ethanol and water in a volume ratio of 1:1, heating to ensure supersaturation, performing rapid suction filtration, and drying; putting the product into a vacuum oven for drying to obtain tetracarboxylazobenzene; the molecular formula of the product is shown as follows:
Figure BDA0001306375870000031
the polyacrylic acid modified by pyrimidinone is used, the main chain of the polyacrylic acid is a main chain connected with carbon and carbon, part of the side chain is carboxyl, part of the side chain is 2-ureido-4 [ 1H ] -pyrimidinone connected with the main chain through carbonyl, and the number average molecular weight of the polyacrylic acid is 400000-800000, preferably 500000-600000.
The pyrimidone-modified polyacrylic acid used was prepared according to the following procedure:
step 1, putting 2-amino-4-carbonyl-6-methylpyrimidine and hexamethylene diisocyanate into a reactor, and carrying out condensation reflux under the condition of nitrogen; adding petroleum ether into the reactant, and performing suction filtration; drying the obtained powder in a vacuum oven to obtain 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group; the structural chemical formula of the product is as follows:
Figure BDA0001306375870000032
in step 1, the mass ratio of 2-amino-4-carbonyl-6-methylpyrimidine to hexamethylene diisocyanate is 1: (6-7).
In the step 1, the condensation reflux temperature is 100-120 ℃, and the time is 14-16 h.
Step 2, dissolving polyacrylic acid in N, N' -dimethylformamide solution, adding 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group into the solution, and carrying out condensation reflux under the condition of nitrogen; adding dibutyltin laurate and stirring the mixture at 50-80 ℃ for at least 1 h; the reaction mass is precipitated by dichloromethane and centrifuged; drying in a vacuum oven to obtain polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidone, namely polyacrylic acid modified based on pyrimidone, and the chemical structural formula is as follows:
Figure BDA0001306375870000041
in step 2, the mass ratio of 2-ureido-4 [ 1H ] -pyrimidone bearing isocyanate groups to polyacrylic acid is (40-160): 1; adding dibutyltin dilaurate and polyacrylic acid in a ratio of 1: (100-200).
In step 2, under nitrogen, the mixture is refluxed at 100-120 ℃ for 20-40 h, preferably 30-40 h.
In step 2, after adding dibutyltin laurate, the mixture is stirred at 60 to 80 ℃ for 1 to 4 hours at a stirring speed of 100 to 150 revolutions per minute.
In step 2, the polyacrylic acid has a number average molecular weight of 400000 to 800000, preferably 500000 to 600000.
In step 2, 15-20mmol of polyacrylic acid is dissolved in 500ml of N, N '-dimethylformamide, and the concentration of polyacrylic acid in the N, N' -dimethylformamide solution is 0.03-0.04 mol/L.
The application of the pyrimidone-based modified polyacrylic acid in preparing the light-driven material is as follows, and the application of the pyrimidone-based modified polyacrylic acid in preparing the self-repairing material is as follows.
The prepared 2-ureido-4 [1 hydrogen ] with isocyanate group]-pyrimidinones, pyrimidinone-modified polyacrylic acids, tetracarboxylazobenzenes and films were subjected to infrared characterization, as shown in the figure. In FIG. 1, 1704cm can be seen-1The position is a stretching vibration peak of a carbon-oxygen double bond in carboxyl of 1400cm-1And 920cm-1The position is a bending vibration absorption peak of a hydrogen-oxygen bond, and carboxyl exists in the structure, which indicates that the tetra-carboxyl azobenzene is successfully synthesized. In FIG. 2, 2279cm-1Is located at 1700cm of isocyanate group stretching vibration peak-1,1765cm-1,1500cm-1,1257cm-1Is the stretching vibration peak of amido bond, the reaction is the reaction of amino and isocyanate group, 3678cm can be seen from the figure-1The amino peak at (A) is indeed disappeared, indicating that 2-ureido-4 [1 hydrogen ] has an isocyanate group]-pyrimidinones were successfully prepared. In FIG. 3, it can be seen that the peak of stretching vibration of the hydroxyl group in the carboxyl group after the reaction was reduced and 1708cm was simultaneously observed-1The stretching vibration peak of the C-O double bond still exists, and the stretching vibration peak of the C-O single bond is weakened to 1533cm-1And 1257cm-1The stretching vibration peak of the amide bond still exists, the reaction does occur and the polyacrylic acid based on the pyrimidone modification is prepared. In FIG. 4, it can be seen that the thickness of the film was 2927cm after the film was formed-1At 1707cm of the peak of stretching vibration with carboxyl-1The position is the stretching vibration peak of carboxyl carbon-oxygen double bond, 1156cm-1、1298cm-1And 1631cm-1Is the stretching vibration peak of amido bond, and the product after film formation has 2-ureido-4 [1 ] hydrogen]-polyacrylic acid and tetracarboxylazobenzene of pyrimidinones without formation of new groups.
For a film of 3cm × 1cm × 30 μm, a light intensity of 350mW/cm and a wavelength of 320-390nm2When the film is irradiated by ultraviolet light, the film is found to curl away from a light source, and after 6 seconds of irradiation, the curling angle is the largest and can reach 120 degrees on average. Cutting a scratch with a thickness of 1cm and a thickness of 12 μm on the film by using a blade, and cutting the film by using a light source with a wavelength of 320-390nm and a light intensity of 350mW/cm2The ultraviolet light is used for irradiation, the scratch can be observed to gradually disappear, and the film can be completely repaired within the shortest timeAll can reach 20min, which proves that the film of the invention has light response and self-repairing performance.
As shown in FIGS. 7 and 8, UPy represents 2-ureido-4 [1 ] hydrogen]-a pyrimidinone; n is used to represent the number of unit segments, i.e., the degree of polymerization;
Figure BDA0001306375870000051
represents a quadruple hydrogen bond; … … denotes hydrogen bonding. The presence of hydrogen bearing 2-ureido-4 [1 ] in the preparation of the film]Polyacrylic and tetracarboxylazobenzenes of pyrimidinones, 2-ureido-4 [1 ] hydro-gen of the polyacrylic side chain]Quadruple hydrogen bonds can be formed between pyrimidinones, hydrogen bonds can be formed between carboxyl groups on tetracarboxylazobenzene, and simultaneously the carboxyl groups on polyacrylic acid and the carboxyl groups on azobenzene can form hydrogen bonds. When the film is damaged, the hydrogen bonds are broken; when ultraviolet light irradiates, azobenzene is changed from a trans form to a cis form, the distance between molecules is shortened, and the distance between polyacrylic acid molecular chains is shortened, so that the film is bent; simultaneously, 2-ureido-4 [1 hydrogen]The pyrimidone absorbs ultraviolet light and converts the ultraviolet light into heat, and the quadruple hydrogen bonds are rearranged, so that the film has a self-repairing function. Finally, the effect of repairing the film while bending under the irradiation of ultraviolet light is realized.
Compared with the prior art, the invention uses polyacrylic acid modified based on pyrimidone and introduces the tetracarboxylazobenzene to realize the film light drive, and introduces the self-repairing characteristic, and utilizes quadruple hydrogen bonds formed between 2-ureido-4 [1 hydrogen ] -pyrimidone and hydrogen bonds formed between the tetracarboxylazobenzene to form supermolecule self-assembly, thereby realizing the self-repairing under the light drive. The preparation method is simple and easy to implement and high in repair efficiency.
Drawings
FIG. 1 is an infrared spectrum of a tetracarboxylic azobenzene prepared in the present invention.
FIG. 2 is an infrared spectrum of 2-ureido-4 [ 1H ] -pyrimidinone having an isocyanate group prepared in the present invention.
FIG. 3 is an infrared spectrum of a polyacrylic acid having 2-ureido-4 [ 1H ] -pyrimidinone prepared in the present invention, wherein (1) is 2-ureido-4 [ 1H ] -pyrimidinone having an isocyanate group, (2) is polyacrylic acid, and (3) is polyacrylic acid having 2-ureido-4 [ 1H ] -pyrimidinone.
FIG. 4 is an infrared spectrum of a film obtained by mixing polyacrylic acid having 2-ureido-4 [ 1H ] -pyrimidinone and tetracarboxylazobenzene according to the present invention.
FIG. 5 is a photo-driven photograph of a film formed by mixing polyacrylic acid having 2-ureido-4 [ 1H ] -pyrimidinone and tetracarboxylazobenzene according to the present invention.
FIG. 6 is an optical microscope photograph showing a repair process of a film after mixing polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidinone and tetracarboxylazobenzene in the present invention.
FIG. 7 is a schematic diagram of the mechanism of photoresponse and self-repair of the film of the present invention (1).
FIG. 8 is a schematic diagram of the mechanism of photoresponse and self-repair of the film of the present invention (2).
Detailed Description
In order to make the advantages, technical means and objects of the present invention more apparent, the present invention will be further described with reference to the following examples. The following examples of the present invention are given to further illustrate the present invention, but not to limit the scope of the present invention. Chemicals were purchased from Tianjin Kewei, Inc. and the testing instrument used the analytical testing platform of Tianjin university.
Example 1
(1) Mixing 2-amino-4-carbonyl-6-methylpyrimidine and hexamethylene diisocyanate according to the weight ratio of 1: 6 mass percent of the mixture is put into a three-neck flask, and the mixture is condensed and refluxed for 16 hours at 100 ℃ under the condition of nitrogen; adding petroleum ether into the reactant, and performing suction filtration; the obtained powder is put into a vacuum oven to be dried, and finally the 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group is obtained.
(2) Dissolving 15mmol of polyacrylic acid with the number average molecular weight of 450000g/mol in 500ml of N, N' -dimethylformamide solution, adding 600mmol of 2-ureido-4 [ 1H ] -pyrimidinone with isocyanate group into the solution, and condensing and refluxing for 40h at 100 ℃ under the condition of nitrogen; adding 0.1mmol of dibutyltin dilaurate, and stirring the mixture at 60 ℃ for 1 h; the reaction mass is precipitated by dichloromethane and centrifuged; drying in vacuum oven to obtain polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidinone.
(3) Dissolving 15mmol of p-aminoisophthalic acid in 40ml of 1mol/L aqueous solution of sodium hydroxide, and adding 15mmol of ammonium nitrite; slowly dripping the solution into 90ml of hydrochloric acid solution, and stirring for 30min at 0 ℃ to obtain diazonium salt; dissolving 15mmol of isophthalic acid into 30ml of 1mol/L sodium hydroxide aqueous solution; keeping the temperature at 0 ℃, slowly adding the obtained diazonium salt into the isophthalic acid alkali solution, and keeping the PH at 9; after stirring overnight, the pH was adjusted to 3 to produce a large amount of precipitate; performing suction filtration, adding a large amount of water, performing suction filtration, and drying; dissolving the product in a mixed solution of ethanol and water in a volume ratio of 1:1, heating to ensure supersaturation, performing rapid suction filtration, and drying; and putting the product into a vacuum oven for drying to obtain the tetracarboxylazobenzene.
(4) Dissolving 6mmol of (2) in the step into 200ml of N, N '-dimethylformamide solution, and dissolving 0.15mmol of (3) into 200ml of N, N' -dimethylformamide solution; stirring for 12 h; and (5) carrying out suction filtration, and taking the obtained filtrate.
(5) Suspending, steaming and concentrating the filtrate to 3ml, dripping the filtrate on a quartz plate, and fully paving; putting into a normal-temperature vacuum oven for 24 hours; and then putting the film into a 60-degree vacuum oven to be dried for 24 hours, and finally obtaining the film.
(6) Cutting a scratch with a thickness of 1cm and a thickness of 12 μm on the film by using a blade, and cutting the film by using a light source with a wavelength of 320-390nm and a light intensity of 350mW/cm2When the ultraviolet light is used for irradiation, the scratch can be observed to gradually disappear, and the shortest time for completely repairing the film is 60 min.
Example 2
(1) Mixing 2-amino-4-carbonyl-6-methylpyrimidine and hexamethylene diisocyanate according to the weight ratio of 1: 6.5 mass ratio, putting into a three-neck flask, and carrying out 110-degree condensation reflux for 15h under the nitrogen condition; adding petroleum ether into the reactant, and performing suction filtration; the obtained powder is put into a vacuum oven to be dried, and finally the 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group is obtained.
(2) 17mmol of polyacrylic acid with the number-average molecular weight of 450000g/mol are dissolved in 500ml of N, N' -dimethylformamide solution, 1.7mol of 2-ureido-4 [ 1H ] -pyrimidinone with isocyanate group is added into the solution, and the solution is condensed and refluxed for 40h at 100 ℃ under the condition of nitrogen; adding 0.17mmol of dibutyltin dilaurate, and stirring the mixture at 60 ℃ for 1 h; the reaction mass is precipitated by dichloromethane and centrifuged; drying in vacuum oven to obtain polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidinone.
(3) Dissolving 15mmol of p-aminoisophthalic acid in 40ml of 1mol/L aqueous solution of sodium hydroxide, and adding 22.5mmol of ammonium nitrite; slowly dripping the solution into 90ml of hydrochloric acid solution, and stirring for 30min at 0 ℃ to obtain diazonium salt; dissolving 15mmol of isophthalic acid into 30ml of 1mol/L sodium hydroxide aqueous solution; keeping the temperature at 0 ℃, slowly adding the obtained diazonium salt into the isophthalic acid alkali solution, and keeping the PH at 9; after stirring overnight, the pH was adjusted to 3 to produce a large amount of precipitate; performing suction filtration, adding a large amount of water, performing suction filtration, and drying; dissolving the product in a mixed solution of ethanol and water in a volume ratio of 1:1, heating to ensure supersaturation, performing rapid suction filtration, and drying; and putting the product into a vacuum oven for drying to obtain the tetracarboxylazobenzene.
(4) Dissolving the step 8mmol of (2) into 200ml of N, N '-dimethylformamide solution, and dissolving 0.4mmol of (3) into 200ml of N, N' -dimethylformamide solution; stirring for 12 h; and (5) carrying out suction filtration, and taking the obtained filtrate.
(5) Suspending, steaming and concentrating the filtrate to 3ml, dripping the filtrate on a quartz plate, and fully paving; putting into a normal-temperature vacuum oven for 24 hours; and then putting the film into a 60-degree vacuum oven to be dried for 24 hours, and finally obtaining the film.
(6) Cutting a scratch with a thickness of 1cm and a thickness of 12 μm on the film by using a blade, and cutting the film by using a light source with a wavelength of 320-390nm and a light intensity of 350mW/cm2When the ultraviolet light is used for irradiation, the scratch can be observed to gradually disappear, and the shortest time for completely repairing the film is 45 min.
Example 3
(1) Mixing 2-amino-4-carbonyl-6-methylpyrimidine and hexamethylene diisocyanate according to the weight ratio of 1: 6 mass percent of the mixture is put into a three-neck flask, and the mixture is condensed and refluxed at 120 ℃ for 14 hours under the condition of nitrogen; adding petroleum ether into the reactant, and performing suction filtration; the obtained powder is put into a vacuum oven to be dried, and finally the 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group is obtained.
(2) Dissolving 20mmol of polyacrylic acid with the number average molecular weight of 450000g/mol in 500ml of N, N' -dimethylformamide solution, adding 3.2mol of 2-ureido-4 [ 1H ] -pyrimidinone with isocyanate group into the solution, and condensing and refluxing for 40h at 100 ℃ under the condition of nitrogen; adding 0.1mmol of dibutyltin dilaurate, and stirring the mixture at 60 ℃ for 1 h; the reaction mass is precipitated by dichloromethane and centrifuged; drying in vacuum oven to obtain polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidinone.
(3) Dissolving 15mmol of p-aminoisophthalic acid in 40ml of 1mol/L aqueous solution of sodium hydroxide, and adding 18.75mmol of ammonium nitrite; slowly dripping the solution into 90ml of hydrochloric acid solution, and stirring for 30min at 0 ℃ to obtain diazonium salt; dissolving 15mmol of isophthalic acid into 30ml of 1mol/L sodium hydroxide aqueous solution; keeping the temperature at 0 ℃, slowly adding the obtained diazonium salt into the isophthalic acid alkali solution, and keeping the PH at 9; after stirring overnight, the pH was adjusted to 3 to produce a large amount of precipitate; performing suction filtration, adding a large amount of water, performing suction filtration, and drying; dissolving the product in a mixed solution of ethanol and water in a volume ratio of 1:1, heating to ensure supersaturation, performing rapid suction filtration, and drying; and putting the product into a vacuum oven for drying to obtain the tetracarboxylazobenzene.
(4) Dissolving the step 7mmol of (2) into 200ml of N, N '-dimethylformamide solution, and dissolving 0.3mmol of (3) into 200ml of N, N' -dimethylformamide solution; stirring for 12 h; and (5) carrying out suction filtration, and taking the obtained filtrate.
(5) Suspending, steaming and concentrating the filtrate to 3ml, dripping the filtrate on a quartz plate, and fully paving; putting into a normal-temperature vacuum oven for 24 hours; and then putting the film into a 60-degree vacuum oven to be dried for 24 hours, and finally obtaining the film.
(6) Cutting a scratch with a thickness of 1cm and a thickness of 12 μm on the film by using a blade, and cutting the film by using a light source with a wavelength of 320-390nm and a light intensity of 350mW/cm2When the ultraviolet light is used for irradiation, the scratch can be observed to gradually disappear, and the shortest time for completely repairing the film is 30 min.
Example 4
(1) Putting 2-amino-4-carbonyl-6-methylpyrimidine and hexamethylene diisocyanate into a three-neck flask according to the mass ratio of 1:7, and carrying out condensation reflux for 15h at 100 ℃ under the condition of nitrogen; adding petroleum ether into the reactant, and performing suction filtration; the obtained powder is put into a vacuum oven to be dried, and finally the 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group is obtained.
(2) 17mmol of polyacrylic acid with the number-average molecular weight of 450000g/mol are dissolved in 500ml of N, N' -dimethylformamide solution, 1.7mol of 2-ureido-4 [ 1H ] -pyrimidinone with isocyanate group is added into the solution, and the solution is condensed and refluxed for 40h at 100 ℃ under the condition of nitrogen; adding 0.11mmol of dibutyltin dilaurate, and stirring the mixture at 60 ℃ for 1 h; the reaction mass is precipitated by dichloromethane and centrifuged; drying in vacuum oven to obtain polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidinone.
(3) Dissolving 15mmol of p-aminoisophthalic acid in 40ml of 1mol/L aqueous solution of sodium hydroxide, and adding 15mmol of ammonium nitrite; slowly dripping the solution into 90ml of hydrochloric acid solution, and stirring for 30min at 0 ℃ to obtain diazonium salt; dissolving 15mmol of isophthalic acid into 30ml of 1mol/L sodium hydroxide aqueous solution; keeping the temperature at 0 ℃, slowly adding the obtained diazonium salt into the isophthalic acid alkali solution, and keeping the PH at 9; after stirring overnight, the pH was adjusted to 3 to produce a large amount of precipitate; performing suction filtration, adding a large amount of water, performing suction filtration, and drying; dissolving the product in a mixed solution of ethanol and water in a volume ratio of 1:1, heating to ensure supersaturation, performing rapid suction filtration, and drying; and putting the product into a vacuum oven for drying to obtain the tetracarboxylazobenzene.
(4) Dissolving the step 8mmol of (2) into 200ml of N, N '-dimethylformamide solution, and dissolving 0.4mmol of (3) into 200ml of N, N' -dimethylformamide solution; stirring for 12 h; and (5) carrying out suction filtration, and taking the obtained filtrate.
(5) Suspending, steaming and concentrating the filtrate to 3ml, dripping the filtrate on a quartz plate, and fully paving; putting into a normal-temperature vacuum oven for 24 hours; and then putting the film into a 60-degree vacuum oven to be dried for 24 hours, and finally obtaining the film.
(6) Cutting a scratch with a thickness of 1cm and a thickness of 12 μm on the film by using a blade, and cutting the film by using a light source with a wavelength of 320-390nm and a light intensity of 350mW/cm2Ultraviolet light is irradiated to observe the scratchThe trace gradually disappeared, and the shortest time for complete repair of the film was 50 min.
Example 5
(1) Mixing 2-amino-4-carbonyl-6-methylpyrimidine and hexamethylene diisocyanate according to the weight ratio of 1: 6.5 mass ratio, putting into a three-neck flask, and carrying out condensation reflux at 110 ℃ for 14h under the nitrogen condition; adding petroleum ether into the reactant, and performing suction filtration; the obtained powder is put into a vacuum oven to be dried, and finally the 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group is obtained.
(2) Dissolving 15mmol of polyacrylic acid with the number average molecular weight of 450000g/mol in 500ml of N, N' -dimethylformamide solution, adding 2-ureido-4 [ 1H ] -pyrimidinone with isocyanate group in an amount which is 40 times of that of the polyacrylic acid into the solution, and condensing and refluxing for 40h at 100 ℃ under the condition of nitrogen; the ratio of the addition amount to the amount of polyacrylic acid material is 100: 1 dibutyltin dilaurate, and then stirring the mixture at 60 ℃ for 1 h; the reaction mass is precipitated by dichloromethane and centrifuged; drying in vacuum oven to obtain polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidinone.
(3) 15mmol of p-aminoisophthalic acid was dissolved in 40ml of a 1mol/L aqueous solution of sodium hydroxide, and ammonium nitrite was added in an amount 1.25 times as much as that of p-aminoisophthalic acid; slowly dripping the solution into 90ml of hydrochloric acid solution, and stirring for 30min at 0 ℃ to obtain diazonium salt; dissolving 15mmol of isophthalic acid into 30ml of 1mol/L sodium hydroxide aqueous solution; keeping the temperature at 0 ℃, slowly adding the obtained diazonium salt into the isophthalic acid alkali solution, and keeping the PH at 9; after stirring overnight, the pH was adjusted to 3 to produce a large amount of precipitate; performing suction filtration, adding a large amount of water, performing suction filtration, and drying; dissolving the product in a mixed solution of ethanol and water in a volume ratio of 1:1, heating to ensure supersaturation, performing rapid suction filtration, and drying; and putting the product into a vacuum oven for drying to obtain the tetracarboxylazobenzene.
(4) Dissolving 6mmol of (2) in the step into 200ml of N, N '-dimethylformamide solution, and dissolving 0.3mmol of (3) into 200ml of N, N' -dimethylformamide solution; stirring for 12 h; and (5) carrying out suction filtration, and taking the obtained filtrate.
(5) Suspending, steaming and concentrating the filtrate to 3ml, dripping the filtrate on a quartz plate, and fully paving; putting into a normal-temperature vacuum oven for 24 hours; and then putting the film into a 60-degree vacuum oven to be dried for 24 hours, and finally obtaining the film.
(6) Cutting a scratch with a thickness of 1cm and a thickness of 12 μm on the film by using a blade, and cutting the film by using a light source with a wavelength of 320-390nm and a light intensity of 350mW/cm2When the ultraviolet light is used for irradiation, the scratch can be observed to gradually disappear, and the shortest time for completely repairing the film is 20 min.
Example 6
(1) Putting 2-amino-4-carbonyl-6-methylpyrimidine and hexamethylene diisocyanate into a three-neck flask according to the mass ratio of 1:7, and carrying out 120-DEG C condensation reflux for 16h under the condition of nitrogen; adding petroleum ether into the reactant, and performing suction filtration; the obtained powder is put into a vacuum oven to be dried, and finally the 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group is obtained.
(2) Dissolving 20mmol of polyacrylic acid with the number average molecular weight of 450000g/mol in 500ml of N, N' -dimethylformamide solution, adding 2-ureido-4 [ 1H ] -pyrimidinone with isocyanate group in 160 times of the amount of the polyacrylic acid into the solution, and condensing and refluxing for 40h at 100 ℃ under the condition of nitrogen; the ratio of the addition amount to the amount of polyacrylic acid material is 200: 1 dibutyltin dilaurate, and then stirring the mixture at 60 ℃ for 1 h; the reaction mass is precipitated by dichloromethane and centrifuged; drying in vacuum oven to obtain polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidinone.
(3) 15mmol of p-aminoisophthalic acid was dissolved in 40ml of a 1mol/L aqueous solution of sodium hydroxide, and ammonium nitrite was added in an amount 1.5 times as much as that of p-aminoisophthalic acid; slowly dripping the solution into 90ml of hydrochloric acid solution, and stirring for 30min at 0 ℃ to obtain diazonium salt; dissolving 15mmol of isophthalic acid into 30ml of 1mol/L sodium hydroxide aqueous solution; keeping the temperature at 0 ℃, slowly adding the obtained diazonium salt into the isophthalic acid alkali solution, and keeping the PH at 9; after stirring overnight, the pH was adjusted to 3 to produce a large amount of precipitate; performing suction filtration, adding a large amount of water, performing suction filtration, and drying; dissolving the product in a mixed solution of ethanol and water in a volume ratio of 1:1, heating to ensure supersaturation, performing rapid suction filtration, and drying; and putting the product into a vacuum oven for drying to obtain the tetracarboxylazobenzene.
(4) Dissolving the step 7mmol of (2) into 200ml of N, N '-dimethylformamide solution, and dissolving 0.15mmol of (3) into 200ml of N, N' -dimethylformamide solution; stirring for 12 h; and (5) carrying out suction filtration, and taking the obtained filtrate.
(5) Suspending, steaming and concentrating the filtrate to 3ml, dripping the filtrate on a quartz plate, and fully paving; putting into a normal-temperature vacuum oven for 24 hours; and then putting the film into a 60-degree vacuum oven to be dried for 24 hours, and finally obtaining the film.
(6) Cutting a scratch with a thickness of 1cm and a thickness of 12 μm on the film by using a blade, and cutting the film by using a light source with a wavelength of 320-390nm and a light intensity of 350mW/cm2When the ultraviolet light is used for irradiation, the scratch can be observed to gradually disappear, and the shortest time for completely repairing the film is 25 min.
The films can be prepared by adjusting the process parameters recorded in the content of the invention, and all show light driving and self-repairing performances. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. The light-driven self-repairing supramolecular film based on multiple hydrogen bonds is characterized by consisting of polyacrylic acid modified based on pyrimidone and tetracarboxylazobenzene, wherein the main chain of the polyacrylic acid modified based on the pyrimidone is a main chain connected with carbon and carbon, partial side chains are carboxyl, and partial side chains are 2-ureido-4 [ 1H ] -pyrimidone connected with the main chain through carbonyl; the ratio of the amounts of substances based on pyrimidone-modified polyacrylic acid and tetracarboxylazobenzene is (15-55): 1; the polyacrylic acid has a number average molecular weight of 400000 to 800000.
2. The multiple hydrogen bond-based photo-actuated self-healing supramolecular film as claimed in claim 1, wherein the ratio of the amounts of pyrimidone-modified polyacrylic acid and tetracarboxylazobenzene-based substances is (20-40): 1.
3. the multiple hydrogen bond-based photo-actuated self-healing supramolecular film in claim 1, wherein polyacrylic acid has a number average molecular weight of 500000 to 600000.
4. The preparation method of the light-driven self-repairing supramolecular film based on multiple hydrogen bonds is characterized by comprising the following steps of: uniformly dispersing tetracarboxylazobenzene and polyacrylic acid based on pyrimidone modification in an organic solvent respectively, dropwise adding an organic solution of polyacrylic acid based on pyrimidone modification into the organic solution of tetracarboxylazobenzene, continuously stirring and dispersing, performing suction filtration to obtain a filtrate, uniformly spreading the filtrate on a substrate, and drying to obtain a film; wherein: the ratio of the amounts of substances based on pyrimidone-modified polyacrylic acid and tetracarboxylazobenzene is (15-55): 1; the polyacrylic acid based on pyrimidone modification has main chain of polyacrylic acid connected with carbon and carbon, partial side chain of carboxyl, partial side chain of 2-ureido-4 [ 1H ] -pyrimidone connected with main chain through carbonyl, and polyacrylic acid number average molecular weight of 400000-800000.
5. The method for preparing multiple hydrogen bond-based photo-driven self-repairing supramolecular membrane as claimed in claim 4, wherein the ratio of the amount of the substance based on the pyrimidone-modified polyacrylic acid to the amount of the substance based on the tetracarboxylazobenzene is (20-40): 1.
6. the method for preparing the multiple hydrogen bond-based photo-driven self-repairing supramolecular film as claimed in claim 4, wherein the organic solvent for dispersing the pyrimidone-modified polyacrylic acid is the same as the organic solvent for dispersing the tetracarboxylazobenzene.
7. The method for preparing the multiple hydrogen bond-based photo-driven self-repairing supramolecular film as claimed in claim 4, wherein the polyacrylic acid has a number average molecular weight of 500000-600000.
8. The preparation method of the multiple hydrogen bond-based photo-driven self-repairing supramolecular film as claimed in claim 4, wherein the filtrate is selected to be suspended, evaporated and concentrated, and then dripped on a quartz plate to be fully paved; putting the mixture into a vacuum oven at the normal temperature of 20-25 ℃ for 20-24 h; and then putting the film into a vacuum oven at 50-60 ℃ for drying for 20-24 h to finally obtain the film.
9. The preparation method of the multiple hydrogen bond-based photo-driven self-repairing supramolecular film as claimed in claim 4, wherein the organic solution based on the pyrimidone modified polyacrylic acid is dripped into the organic solution of the tetracarboxylazobenzene at a dripping speed of 1-3 ml per minute and is continuously stirred and dispersed for 10-12 hours.
10. The preparation method of the multiple hydrogen bond-based photo-driven self-repairing supramolecular film as claimed in claim 4, wherein the preparation method is based on pyrimidone modified polyacrylic acid and comprises the following steps:
step 1, putting 2-amino-4-carbonyl-6-methylpyrimidine and hexamethylene diisocyanate into a reactor, and carrying out condensation reflux under the condition of nitrogen; adding petroleum ether into the reactant, and performing suction filtration; drying the obtained powder in a vacuum oven to obtain 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group; in step 1, the mass ratio of 2-amino-4-carbonyl-6-methylpyrimidine to hexamethylene diisocyanate is 1: (6-7); the condensation reflux temperature is 100-120 ℃, and the time is 14-16 h;
step 2, dissolving polyacrylic acid in N, N' -dimethylformamide solution, adding 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group into the solution, and condensing and refluxing for 20-40 h at 100-120 ℃ under the condition of nitrogen; adding dibutyltin laurate, and then stirring the mixture for at least 1h at the temperature of between 50 and 80 ℃, wherein the stirring speed is between 100 and 150 revolutions per minute; the reaction mass is precipitated by dichloromethane and centrifuged; drying in a vacuum oven to obtain polyacrylic acid with 2-ureido-4 [ 1H ] -pyrimidinone, namely polyacrylic acid modified based on pyrimidinone; the mass ratio of 2-ureido-4 [ 1H ] -pyrimidone with isocyanate group and polyacrylic acid is (40-160) to 1; adding dibutyltin dilaurate and polyacrylic acid in a ratio of 1: (100-200).
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