CN110343202B - Preparation method of photo-repairable azobenzene polymer - Google Patents

Preparation method of photo-repairable azobenzene polymer Download PDF

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CN110343202B
CN110343202B CN201910659981.3A CN201910659981A CN110343202B CN 110343202 B CN110343202 B CN 110343202B CN 201910659981 A CN201910659981 A CN 201910659981A CN 110343202 B CN110343202 B CN 110343202B
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azobenzene
anthracene
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oxyacetic
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薛小强
梁康
蒋必彪
黄文艳
杨宏军
蒋其民
江力
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Changzhou University
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    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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Abstract

The invention belongs to the technical field of high molecular materials, and particularly relates to a photo-repairable azobenzene polymer and a preparation method thereof. Firstly, obtaining a monomer containing anthracene and azobenzene groups, 4 '- (hexyl methacrylate oxy) -4- (oxyacetic acid anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) by carrying out etherification, nitro reduction, diazo coupling, esterification and other multi-step reactions on nitrophenol, and then carrying out free radical polymerization on the MMA-AZO-AN serving as a monomer under the condition that AN initiator exists to prepare the poly-4' - (hexyl methacrylate oxy) -4- (oxyacetic acid anthracene-2-carbomethoxy) azobenzene. An anthracene group is combined to generate a reversible Diels-Alder addition reaction under a light excitation condition, azobenzene generates a reversible cis-trans isomerization behavior under the excitation of ultraviolet light and visible light, and the cooperation of two photoresponse structures is applied to prepare the novel photo-repairable azobenzene polymer.

Description

Preparation method of photo-repairable azobenzene polymer
Technical Field
The invention belongs to the technical field of high molecular materials, and particularly relates to a preparation method of a photo-repairable azobenzene polymer.
Background
The polymer and the composite material thereof can be subjected to chemical erosion, mechanical scratch or impact, thermal decomposition and other environmental influences in the long-term use process to generate micro cracks, so that the material is finally damaged, and the service life of the material is shortened. This is also a direct cause of the deterioration of the properties of the material in use. Conventional repair methods such as welding, gluing, and sewing are only parts that re-bond or enhance damage to the polymeric material on a macroscopic level. The self-repairing function is introduced into the polymer material, so that the material can be automatically repaired after damage is generated inside the material, and the structural material with longer service life, more reliable performance and more economical efficiency is obtained. For example, in microelectronic polymer devices and adhesive applications, performance loss due to microcracks generated by thermal and mechanical fatigue is a long-standing problem, and the introduction of self-healing functions into these materials can greatly improve the reliability and service life of microelectronic products. The research of the self-repairing material is beneficial to obtaining the material with the bionic effect, has application prospect in the field of biological medical treatment, and can obtain more durable human body joints. The research on the self-repairing material is helpful for developing materials with special purposes, such as materials capable of recovering the properties of interface, electric conduction, heat conduction and the like under certain conditions, and the research on the self-repairing of micron and submicron gaps for realizing the recovery of the interface property or the conduction property is more concerned. The method is particularly important in the fields of aerospace and the like.
The development of the diversification of the repair materials has been in progress for decades, and the repair process can be divided into an automatic repair system and a non-automatic repair system according to whether external factors are needed to promote the repair process. The automatic repair system is typically represented by a microcapsule system, and mainly means that a certain amount of monomer (repair agent) and initiator (catalyst) are added into a material, the monomer (repair agent) and the initiator (catalyst) are separated and dispersed in the material, once a crack occurs in the material, the microcapsule is broken, the monomer and the initiator are mixed in the crack and rapidly undergo a polymerization reaction, so that a new polymer is formed at the crack generated by the fracture of the material, and the repair of the material is completed. The repairing method is simple and high in repairing efficiency, but has the biggest defects that the repairing can be realized only once, and the Grubb catalyst is expensive and has the possibility of deactivation. Then White et al developed a microvascular self-healing system with a three-dimensional network structure, which can achieve multiple-cycle healing, but the preparation process is relatively complicated and expensive. The diene compound mainly utilizes the reversible chemical reaction in the polymer material to realize the self-repair of the material, and can carry out multiple times of circulating repair at the same position of the material, but the repair process can be carried out only by the stimulation of external conditions, such as light, heat, chemical action and the like. There are two main classes based on the type of reversible chemical bonds: (1) reversible non-covalent bond: hydrogen bonding, pi-pi stacking metal-ligand coordination; (2) reversible covalent bond: Diels-Alder (DA) reaction adduct. Diels-Alder is a typical reversible reaction. The Diels-Alder reaction has the advantages of mild condition, high yield, no need of catalyst, less side reaction and reversible property, and can be used for preparing polymer repairing materials.
The azobenzene compound is a compound in which aromatic rings are connected by a nitrogen-nitrogen double bond. Under the action of ultraviolet light or heat, the azobenzene can generate reversible cis-trans isomerization. The carbon distance dimension of azobenzene is trans-form under the irradiation of ultraviolet light
Figure BDA0002138198750000021
Become cis-form
Figure BDA0002138198750000022
The dipole moment changes from 0D in trans to 3D in cis, the reaction equation is as follows:
Figure BDA0002138198750000023
the azobenzene polymer is formed by introducing azobenzene groups into the polymer by doping or chemical bonding. Compared with small organic molecules, the azobenzene polymer has remarkable advantages in the aspects of mechanical property, processability, thermal stability, film forming property and the like. The azobenzene polymer has the advantages of photoinduced cis-trans isomerization performance, excellent mechanical property and processing performance, and great application potential in the fields of molecular switches, liquid crystal materials, optical drive and the like.
Disclosure of Invention
Although the azobenzene polymer has photoisomerization, the polymer chain has certain migration under the action of light, but the damaged surface has a repairing function. The anthracene group is a super-conjugated system formed by connecting triphenyl, so that the anthracene group has an obvious ultraviolet absorption peak, strong fluorescence emission and high photoreaction activity. Therefore, the anthracene structure is introduced into the side chain of the azobenzene polymer to prepare the anthracene-containing azobenzene polymer, reversible Diels-Alder (DA) addition reaction is carried out on the anthracene group under the excitation condition of light (365nm and 254nm), reversible cis-trans isomerization action is carried out on the azobenzene under the excitation of ultraviolet light and visible light, and the cooperation of the two photoresponse structures is applied to prepare the novel photo-repairable azobenzene polymer.
Firstly, a monomer containing anthracene and azobenzene groups, namely 4' - (hexyl methacrylate oxy) -4- (oxyacetic acid anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) is synthesized by a multi-step reaction method. Then, MMA-AZO-AN is used as a monomer, Azobisisobutyronitrile (AIBN) or dibenzoyl peroxide (BPO) is used as AN initiator, and conventional free radical polymerization is carried out to prepare poly 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (PMMA-AZO-AN).
The most important photochemical reaction of anthracene group is [4+4] photodimerization reaction under the excitation condition of long wavelength ultraviolet light (365nm), and is ultraviolet light Diels-Alder (DA) addition reaction, and the obtained dimer can be reduced to produce anthracene group under the condition of short wavelength (254 nm). The photodimerization reaction is used for photocrosslinking and decrosslinking groups in the polymer, and the photorepairing groups can be used in the repairing material.
The reversible reaction of anthracene is as follows:
Figure BDA0002138198750000041
the invention adopts the following technical scheme:
the structural general formula of the photo-repairable azobenzene polymer (PMMA-AZO-AN) is as follows:
Figure BDA0002138198750000042
in the formula: n is an integer, the molecular weight is 3000-100000, and PDI is 1.3-2.5.
The PMMA-AZO-AN is obtained by conventional free radical polymerization of 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN), Azobisisobutyronitrile (AIBN) or dibenzoyl peroxide (BPO) is used as AN initiator, a solvent can be a good solvent such as Tetrahydrofuran (THF), N-dimethylformamide, acetone, anisole, toluene and the like, the polymerization temperature is 50-100 ℃, the dosage of AIBN or BPO is 1% of the mole number of a monomer, and the PMMA-AZO-AN is obtained by purification after the reaction is finished.
The 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) has the following structural general formula:
Figure BDA0002138198750000043
the MMA-AZO-AN is prepared by the steps of etherification, nitro reduction, diazo coupling, esterification, substitution, reesterification and the like of p-nitrophenol, and the reaction equation is as follows:
Figure BDA0002138198750000051
the preparation method of MMA-AZO-AN comprises the following steps: firstly, preparing 4-hydroxy hexyloxy azophenol; then, 2-bromoacetic acid anthracene-10-ylmethyl ester is prepared; and finally, substituting 4-hydroxyhexyloxy azophenol and anthracene-10-ylmethyl 2-bromoacetate to prepare 4 '- (hydroxyhexyloxy) -4- (oxyacetic acid anthracenemethyl) azobenzene, and performing esterification to prepare a monomer containing anthracene and azobenzene groups, namely 4' - (hexylmethacrylate oxy) -4- (oxyacetic acid anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN).
The preparation method of the 4-hydroxyhexyloxy azophenol comprises the following steps:
(1) reacting 6-chlorohexanol and p-nitrophenol in the presence of inorganic base and KI as a catalyst to prepare an intermediate p-nitrophenoxyhexanol, wherein the molar ratio of the 6-chlorohexanol to the p-nitrophenol is 0.5-2:1, and the inorganic base is K2CO3Or Na2CO3The dosage of the compound is 1.24 times of the molar weight of the p-nitrophenol; the KI consumption is 0.08 percent of the mass of the p-nitrophenol, and the reaction conditions are as follows: DMF is taken as a solvent, reflux reaction is carried out at 120 ℃ for 6 hours and then the reaction is stopped,recrystallizing with ethanol to obtain intermediate;
(2) p-Nitrophenoxyhexanol in reducing agent Fe/NH4Reducing in the presence of Cl to prepare an intermediate p-aminophenoxy hexanol; wherein the dosage of the reducing agent Fe is 1-10 times of the molar weight of the p-nitrophenoxyhexanol, Fe and NH4The mol ratio of Cl is 1: 1-3;
(3) diazotizing amino phenoxy hexanol under the action of an oxidant sodium nitrite, and performing coupling reaction with phenol to prepare an intermediate 4-hydroxy hexyloxy azophenol; the method comprises the following steps of (1) carrying out diazo coupling reaction at 0-5 ℃, carrying out ethanol recrystallization and drying to obtain an intermediate, wherein the molar ratio of p-aminophenoxy hexanol to phenol is 1: 1-2, the use amount of sodium nitrite is 1-2 times of the molar amount of phenol;
the preparation method of the 2-bromoacetic acid anthracene-10-methyl ester comprises the following steps: esterifying anthracene methanol and bromoacetyl bromide in the presence of an acid-binding agent at 0-5 ℃ to prepare an intermediate 2-bromoacetic acid anthracene-10-yl methyl ester; wherein, the molar ratio of the anthracene methanol to the bromoacetyl bromide is 1: 1-1.5, and triethylamine is used as an acid-binding agent, wherein the dosage of the triethylamine is 1-1.5 times of the molar weight of bromoacetyl bromide.
The preparation method of the 4' - (hydroxyhexyloxy) -4- (oxyacetic acid anthracenyl) azobenzene comprises the following steps: 2-bromoacetic acid anthracene-10-methyl ester and 4-hydroxy hexyloxy azophenol are subjected to substitution reaction to prepare an intermediate 4' - (hydroxy hexyloxy) -4- (oxyacetic acid anthracene carbomethoxy) azobenzene; wherein the molar ratio of 2-bromoacetic acid anthracene-10-methyl ester to 4-hydroxy hexyloxy azophenol is 1-1.5: 1, the reaction condition is reflux reaction at 60 ℃ for 5 hours, and the product is prepared by ethanol recrystallization.
The preparation method of the 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) comprises the following steps: 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracene carbomethoxy) azobenzene and methacryloyl chloride are esterified at low temperature to prepare the compound; wherein the mol ratio of 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracenyl) azobenzene to methacryloyl chloride is 1: 1-1.5, slowly dripping methacryloyl chloride into the reaction solution through a constant-pressure dropping funnel under the esterification reaction condition of 0-5 ℃, and recrystallizing with ethanol after 5 hours.
Has the advantages that:
the anthracene-containing azobenzene polymer material prepared by the invention has the characteristics of excellent photocrosslinking and decrosslinking of an anthracene structure under light irradiation, and azobenzene has excellent characteristics under photoisomerization under light irradiation, and has a synergistic effect of azobenzene isomerization and anthracycline addition on a polymer film through light irradiation along with polymeric chain mobility, so that the broken polymer surface has a light repairing property.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum (CDCl) of purified p-nitrophenoxyhexanol3Is a solvent);
FIG. 2 is a nuclear magnetic hydrogen spectrum of purified p-aminophenoxy hexanol (deuterated DMSO as a solvent);
FIG. 3 is a nuclear magnetic hydrogen spectrum of purified 4-hydroxyhexyloxy azophenol (deuterated DMSO as a solvent);
FIG. 4 is a nuclear magnetic hydrogen spectrum (CDCl) of purified anthracene-10-ylmethyl 2-bromoacetate3Is a solvent);
FIG. 5 is a nuclear magnetic hydrogen spectrum (CDCl) of purified 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracenemethylcarbonyl) azobenzene3Is a solvent);
FIG. 6 is a high performance liquid chromatogram of purified 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN);
FIG. 7 nuclear magnetic hydrogen spectrum (CDCl) of purified 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN)3Is a solvent);
FIG. 8, Polymer PMMA-AZO-AN (M)n＝3.18×104g/mol, PDI 1.86).
FIG. 9, Polymer PMMA-AZO-AN (M)n＝3.18×104g/mol, PDI 1.86).
Detailed Description
The invention is further illustrated by the following examples:
example 1
Synthesis of p-nitrophenoxyhexanol, prepared by reacting 6-chlorohexanol with p-nitrophenol.
6-Chlorohexanol (37.0mmol, 5.05g), 4-nitrophenol (44.4mmol, 6.18g), K2CO3(55.4mmol, 7.65g), KI (5mg) and DMF (50mL) were added to a three-necked flask, refluxed at 120 ℃ and reacted for 6 hours, and then the reaction was stopped, and the mixed solution was poured into a large amount of water to obtain an off-white precipitate, which was recrystallized by filtration with ethanol and dried to obtain p-nitrophenoxyhexanol with a yield of about 87% and a purity of 95% by HPLC.
FIG. 1 is a nuclear magnetic hydrogen spectrum (CDCl) of purified p-nitrophenoxyhexanol3As a solvent). Peaks at chemical shifts 8.08ppm and 6.99ppm correspond to proton peak (a, b) at the benzene ring carbon, peak at chemical shift 4.08ppm corresponds to proton peak (c) at methylene group linked to oxygen, peak at chemical shift 3.72ppm corresponds to proton peak (g) at methylene group linked to hydroxyl group, peaks at chemical shifts 1.89ppm, 1.66ppm and 1.51ppm are proton peaks (d, f, e) at methylene group, and peak at chemical shift 1.29ppm is proton peak (h) at hydroxyl group. The peak areas at a, b, c, d, e, f, g and h are integrated, the area ratio is 2.00:2.06:2.12:2.18:4.24:2.08:2.08:1.02, and the result is consistent with a theoretical value, so that the p-nitrophenoxyhexanol is successfully prepared.
Example 2
Synthesis of p-nitrophenoxyhexanol
6-Chlorohexanol (22.2mmol, 3.03g), 4-nitrophenol (44.4mmol, 6.18g), K2CO3(55.4mmol, 7.65g), KI (5mg) and DMF (50mL) were added to a three-necked flask, refluxed at 120 ℃ and reacted for 6 hours, and then the reaction was stopped, and the mixed solution was poured into a large amount of water to obtain an off-white precipitate, which was recrystallized by filtration with ethanol and dried to obtain p-nitrophenoxyhexanol with a yield of about 89% and a purity of 95% by HPLC.
Example 3
Synthesis of p-nitrophenoxyhexanol
6-Chlorohexanol (88.8mmol, 12.12g), 4-nitrophenol (44.4mmol, 6.18g), K2CO3(55.4mmol, 7.65g), KI (5mg) and DMF (50mL) were added to a three-necked flask, refluxed at 120 ℃ for 6 hours, and then stopped, and the mixed solution was poured into a large amount of water to obtain riceWhite precipitate, filtering ethanol for recrystallization and drying to obtain p-nitrophenoxyhexanol with the yield of about 85 percent and the purity of 96 percent by high performance liquid chromatography analysis.
Example 4
Synthesizing p-aminophenoxy hexanol, and carrying out reduction reaction on p-nitrophenoxy hexanol to obtain the p-aminophenoxy hexanol.
Ammonium chloride (83.7mmol, 4.48g) was dissolved in deionized water (40mL) and iron powder (50.5mmol, 2.80g) was added to a three-necked flask. P-nitrophenoxyhexanol (16.7mmol, 4.0g) was dissolved in 140mL of methanol and then added to a rapidly stirred three-necked flask to conduct nitro reduction. After reacting for 3h at room temperature, the reaction was carried out at 50 ℃ and the progress of the reaction was followed. And after the reaction is finished, filtering to remove iron powder, performing rotary evaporation to remove methanol, performing suction filtration to remove deionized water, performing ethanol recrystallization, and drying to obtain the p-aminophenoxy hexanol, wherein the purity of the high performance liquid chromatography is 95%, and the yield is about 65%.
FIG. 2 is a nuclear magnetic hydrogen spectrum of purified p-aminophenoxyhexanol (deuterated DMSO as solvent). Peaks at chemical shifts 6.52ppm and 6.64ppm correspond to the proton peak (a, b) at the carbon of the benzene ring, the peak at chemical shift 3.79ppm corresponds to the proton peak (c) of the methylene group linked to oxygen, the peak at chemical shift 3.39ppm corresponds to the proton peak (d) of the methylene group linked to the hydroxyl group, the peaks at chemical shifts 1.65ppm, 1.44ppm and 1.36ppm are the proton peaks (e, f, g) of the methylene group, the peak at chemical shift 4.68ppm is the proton peak (h) of the amino group, and the peak at chemical shift 4.37ppm is the characteristic absorption peak (i) of hydrogen at the hydroxyl group. The area ratio of the area integration of the peak areas at a, b, c, d, e, f, g, h and i is 1.92:1.91:1.94:1.83:1.97:2.05:4.06:1.83:1.00, which is consistent with the theoretical value, and the successful preparation of the p-aminophenoxy hexanol is proved.
Example 5
Synthesizing p-aminophenoxy hexanol, and carrying out reduction reaction on p-nitrophenoxy hexanol to obtain the p-aminophenoxy hexanol.
Ammonium chloride (16.7mmol, 0.90g) was dissolved in deionized water (40mL) and iron powder (16.7mmol, 0.56g) was added to the three-necked flask. P-nitrophenoxyhexanol (16.7mmol, 4.0g) was dissolved in 140mL of methanol and then added to a rapidly stirred three-necked flask to conduct nitro reduction. After reacting for 3h at room temperature, the reaction was carried out at 50 ℃ and the progress of the reaction was followed. And after the reaction is finished, filtering to remove iron powder, performing rotary evaporation to remove methanol, performing suction filtration to remove deionized water, performing ethanol recrystallization, and drying to obtain the p-aminophenoxy hexanol, wherein the purity of the high performance liquid chromatography is 95%, and the yield is about 45%.
Example 6
Synthesizing p-aminophenoxy hexanol, and carrying out reduction reaction on p-nitrophenoxy hexanol.
Ammonium chloride (501.0mmol, 27.0g) was dissolved in deionized water (80mL) and iron powder (167.0mmol, 5.6g) was added to a three-necked flask. P-nitrophenoxyhexanol (16.7mmol, 4.0g) was dissolved in 240mL of methanol and then added to a rapidly stirred three-necked flask to conduct a nitro reduction reaction. After reacting for 3h at room temperature, the reaction was carried out at 50 ℃ and the progress of the reaction was followed. And after the reaction is finished, filtering to remove iron powder, performing rotary evaporation to remove methanol, performing suction filtration to remove deionized water, performing ethanol recrystallization, and drying to obtain the p-aminophenoxy hexanol, wherein the purity of the high performance liquid chromatography is 95%, and the yield is about 75%.
Example 7
Synthesizing 4-hydroxy hexyloxy azophenol, and carrying out diazo coupling reaction on p-aminophenoxy hexanol.
P-aminophenoxyhexanol (9.0mmol, 2.6g) was added to a three-necked flask. Hydrochloric acid (2.7mL) was diluted with water (8.0mL) and poured into a three-necked flask. Adding NaNO2An aqueous solution (9.0mmol, 0.62g) was slowly dropped into a three-necked flask via an isopiestic dropping funnel, and diazotization was carried out under ice-bath conditions (0 to 5 ℃). After completion of the reaction, a solution containing phenol (9.0mmol, 0.84g), NaOH (10.8mmol, 0.43g) and Na was added dropwise to the reaction mixture by filtration2CO3(17.8mmol，1.89g)、NaHCO3(17.8mmol, 1.50g) in an aqueous solution, the coupling reaction was carried out while adjusting the pH to 8-9. After the reaction is finished, carrying out suction filtration, recrystallizing by using ethanol, and drying to obtain the 4-hydroxyhexyloxy azophenol. The purity by HPLC analysis was 95% and the yield was about 70%.
FIG. 3 is a nuclear magnetic hydrogen spectrum of purified 4-hydroxyhexyloxyazophenol (deuterated DMSO is a solvent), peaks at chemical shifts of 7.80ppm, 7.75ppm, 7.11ppm and 6.93ppm are characteristic absorption peaks (g, h, f, i) of hydrogen on a benzene ring, a peak at chemical shift of 4.07ppm is a proton peak (e) of a methylene group connected with oxygen, a peak at chemical shift of 3.41ppm is a proton peak (a) of a methylene group connected with a hydroxyl group, peaks at chemical shifts of 1.70ppm, 1.45ppm and 1.40ppm are proton peaks (d, b and c) of a methylene group, and peaks at chemical shifts of 4.37ppm and 10.20ppm are proton peaks (k and j) of a hydroxyl group. The area ratio of the areas of the peaks at a, b, c, d, e, f, g, h, i, j and k is 1.96:1.96:3.62:2.05:1.91:1.83:1.74:1.76:1.79:0.95:1.00, which is consistent with the theoretical value, and the successful preparation of the 4-hydroxyhexyloxy azophenol is proved.
Example 8
Synthesizing 4-hydroxy hexyloxy azophenol, and carrying out diazo coupling reaction on p-aminophenoxy hexanol.
P-aminophenoxyhexanol (9.0mmol, 2.6g) was added to a three-necked flask. Hydrochloric acid (2.7mL) was diluted with water (8.0mL) and poured into a three-necked flask. Adding NaNO2An aqueous solution (13.5mmol, 0.93g) was slowly dropped into a three-necked flask via a constant pressure dropping funnel, and diazotization was carried out under ice bath (0 to 5 ℃). After completion of the reaction, a solution containing phenol (13.5mmol, 1.26g), NaOH (16.2mmol, 0.64g) and Na was added dropwise to the reaction mixture by filtration2CO3(17.8mmol，1.89g)、NaHCO3(17.8mmol, 1.50g) in an aqueous solution, the coupling reaction was carried out while adjusting the pH to 8-9. After the reaction is finished, carrying out suction filtration, recrystallizing by using ethanol, and drying to obtain the 4-hydroxyhexyloxy azophenol. The purity by HPLC was 96% and the yield was about 72%.
Example 9
4-hydroxy hexyloxy azophenol, and the diazo coupling reaction of p-aminophenoxy hexanol.
P-aminophenoxyhexanol (9.0mmol, 2.6g) was added to a three-necked flask. Hydrochloric acid (2.7mL) was diluted with water (8.0mL) and poured into a three-necked flask. Adding NaNO2An aqueous solution (18.0mmol, 12.4g) was slowly dropped into a three-necked flask via a constant pressure dropping funnel, and diazotization was carried out under ice bath (0 to 5 ℃). After completion of the reaction, a solution containing phenol (18.0mmol, 1.68g), NaOH (21.6mmol, 0.86g) and Na was added dropwise to the reaction mixture by filtration2CO3(17.8mmol，1.89g)、NaHCO3(17.8mmol, 1.50g) in an aqueous solution, the coupling reaction was carried out while adjusting the pH to 8-9. After the reaction is finished, carrying out suction filtration, recrystallizing by using ethanol, and drying to obtain the 4-hydroxyhexyloxy azophenol. The purity by HPLC analysis was 95% and the yield was about 75%.
Example 10
Synthesizing 2-bromoacetic acid anthracene-10-methyl ester, and esterifying anthracene methanol and bromoacetyl bromide at low temperature.
Bromoacetyl bromide (11.5mmol, 1.0mL) is dissolved in 10mL dichloromethane, and slowly dropped into a round-bottomed flask containing anthracene methanol (9.7mmol, 2.01g) and triethylamine (12.5mmol, 1.26g) in tetrahydrofuran solution (10mL) through an isopiestic dropping funnel under the condition of ice bath (0-5 ℃), and after the reaction is finished, the obtained solution is washed, dried and recrystallized by ethanol to obtain 2-bromoacetic acid anthracene-10-ylmethyl ester. The purity of HPLC analysis was 95%, and the yield was about 60%.
FIG. 4 is a nuclear magnetic hydrogen spectrum of purified anthracene-10-ylmethyl 2-bromoacetate, for which the peaks at chemical shifts δ 8.54ppm, 8.31ppm, 8.06ppm, 7.58ppm, and 7.51ppm correspond to the proton peaks (a-e) of the carbons on the anthracycline, the proton peak at chemical shift δ 6.27ppm corresponds to the carbon attached to the anthracycline, and the proton peak at chemical shift δ 4.70ppm corresponds to the carbon attached to the bromine atom. The area ratio of a, b, c, d, e, f and g is 0.5: 0.99:1.01: 1.00:1.00:1.04:1.00, which corresponds to the theoretical value, and 2-bromoacetic acid anthracen-10-ylmethyl ester was successfully prepared.
Example 11
Synthesizing 2-bromoacetic acid anthracene-10-methyl ester, and esterifying anthracene methanol and bromoacetyl bromide at low temperature.
Bromoacetyl bromide (9.7mmol, 0.8mL) is dissolved in 10mL dichloromethane, and slowly dropped into a round-bottomed flask containing anthracene methanol (9.7mmol, 2.01g) and triethylamine (9.7mmol, 0.98g) in tetrahydrofuran (10mL) through an isopiestic dropping funnel under the condition of ice bath (0-5 ℃), and after the reaction is finished, the obtained solution is washed, dried and recrystallized by ethanol to obtain 2-bromoacetic acid anthracene-10-ylmethyl ester. The purity by HPLC was 96% and the yield was about 56%.
Example 12
Synthesizing 2-bromoacetic acid anthracene-10-methyl ester, and esterifying anthracene methanol and bromoacetyl bromide at low temperature.
Bromoacetyl bromide (14.5mmol, 1.3mL) is dissolved in 10mL dichloromethane, and slowly dropped into a round-bottomed flask containing anthracene methanol (9.7mmol, 2.01g) and triethylamine (14.5mmol, 1.46g) in tetrahydrofuran (10mL) through an isopiestic dropping funnel under the condition of ice bath (0-5 ℃), and after the reaction is finished, the obtained solution is washed, dried and recrystallized by ethanol to obtain 2-bromoacetic acid anthracene-10-ylmethyl ester. The purity by HPLC analysis was 95% and the yield was about 63%.
Example 13
4' - (hydroxyhexyloxy) -4- (oxyacetic acid anthracenemethyl) azobenzene is synthesized by substitution reaction of 4-hydroxyhexyloxy azophenol and 2-bromoacetic acid anthracene-10-ylmethyl ester.
4-Hydroxyhexyloxyazophenol (3.8mmol, 1.19g), anthracen-10-ylmethyl 2-bromoacetate (3.9mmol, 1.29g), K2CO3(4.5mmol, 0.62g) and acetone (30mL) were added sequentially to a round-bottomed flask and the reaction was refluxed at 60 ℃ for 5 hours. After the reaction is finished, inorganic salt is removed by filtration, rotary evaporation and ethanol recrystallization are carried out, and the azobenzene of the product 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracenyl methyl ester group) azobenzene is obtained. The purity by HPLC analysis was 95% and the yield was about 70%.
FIG. 5 is a nuclear magnetic hydrogen spectrum of 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracenyl) azobenzene, for which the peaks at chemical shifts δ 8.53ppm, 8.32ppm, 8.05ppm, 7.57ppm and 7.50ppm correspond to proton peaks (a-e) of carbons on the anthracycline, at chemical shift δ 6.32ppm to proton peak (f) of carbons attached to the anthracycline, at chemical shift δ 4.70ppm to proton peak (g) of carbons attached to the ester group, at chemical shifts δ 7.86ppm and 6.98ppm to proton peaks (h, i) of carbons above the azobenzene ring, at chemical shifts δ 4.04ppm, 3.67ppm, 1.63ppm, 1.50ppm and 1.84ppm (j-o) to proton peak of 6 carbons between azobenzene and methacrylate. The final chemical shift δ 1.25ppm corresponds to the proton absorption peak of the terminal hydroxyl group. The ratio of the areas of a, b, c, d, e, f, g, h, i, j, k, l, m, n and o is 1.00:0.92:0.95:0.98:0.50: 1.00: 1.09:1.95:1.95:1.05:1.02: 2.16: the ratio of 0.97:1.09:0.55 is in accordance with the theoretical value, and 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracenemethylcarbonyl) azobenzene is successfully prepared.
Example 14
4' - (hydroxyhexyloxy) -4- (oxyacetic acid anthracenemethyl) azobenzene is synthesized by substitution reaction of 4-hydroxyhexyloxy azophenol and 2-bromoacetic acid anthracene-10-ylmethyl ester.
4-Hydroxyhexyloxyazophenol (3.8mmol, 1.19g), anthracen-10-ylmethyl 2-bromoacetate (4.6mmol, 1.75g), K2CO3(5.0mmol, 0.69g) and acetone (30mL) were added sequentially to a round-bottomed flask and the reaction was refluxed at 60 ℃ for 5 hours. After the reaction is finished, inorganic salt is removed by filtration, rotary evaporation and ethanol recrystallization are carried out, and the azobenzene of the product 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracenyl methyl ester group) azobenzene is obtained. The purity by HPLC analysis was 95% and the yield was about 75%.
Example 15
4' - (hydroxyhexyloxy) -4- (oxyacetic acid anthracenemethyl) azobenzene is synthesized by substitution reaction of 4-hydroxyhexyloxy azophenol and 2-bromoacetic acid anthracene-10-ylmethyl ester.
4-Hydroxyhexyloxyazophenol (3.8mmol, 1.19g), anthracen-10-ylmethyl 2-bromoacetate (5.7mmol, 1.88g), K2CO3(6.0mmol, 0.83g) and acetone (30mL) were added sequentially to a round-bottomed flask and the reaction was refluxed at 60 ℃ for 5 hours. After the reaction is finished, inorganic salt is removed by filtration, rotary evaporation and ethanol recrystallization are carried out, and the azobenzene of the product 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracenyl methyl ester group) azobenzene is obtained. The purity of HPLC analysis was 95%, and the yield was about 80%.
Example 16
Synthesizing a monomer 4 '- (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN), and esterifying 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracene carbomethoxy) azobenzene and methacryloyl chloride at low temperature.
4' - (hydroxyhexyloxy) -4- (Anthranyloxy acetoacetate) azobenzene (0.74mmol, 0.42g) and triethylamine (1.2mmol, 0.12g) were dissolved in 10mL tetrahydrofuran to prepare a reaction solution, which was then placed in a round-bottomed flask. Methacryloyl chloride (1.0mmol, 0.1mL) was dissolved in 10mL of tetrahydrofuran and slowly dropped into the reaction solution through a constant pressure dropping funnel under an ice bath (0-5 ℃). After the reaction is finished for 5h, washing, drying, rotary evaporation and ethanol recrystallization are carried out, and the monomer 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) is obtained. As shown in FIG. 6, high performance liquid chromatography gave a purity of 96.3% with a yield of about 60%.
FIG. 7 is a nuclear magnetic hydrogen spectrum of monomer 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) for which the peaks at chemical shifts δ 8.52ppm, 8.29ppm, 8.02ppm, 7.56ppm and 7.49ppm correspond to proton peaks (a-e) of carbon on the anthracycline, at δ 6.31ppm correspond to proton peak (f) of carbon attached to the anthracycline, at δ 4.70ppm correspond to proton peak (g) of carbon attached to the ester group, at δ 7.81ppm and 6.96ppm correspond to proton peaks (h, i) of carbon above the benzene ring of azobenzene, at δ 4.14ppm, 4.02ppm, 1.49ppm, 1.72ppm and 1.80ppm correspond to proton peaks (j-n) of the middle 6 carbons of azobenzene and methacrylate. Chemical shifts δ 1.94ppm correspond to the proton peak (q) of the methyl group attached to the carbon-carbon double bond, and the final chemical shifts δ 5.54ppm and 6.09ppm correspond to the two proton peaks (o, p) at different positions on the carbon-carbon double bond. The area ratio of a, b, c, d, e, f, g, h, i, j, k, l, m, n, o, p and q is as follows: 2.05:2.08:2.06:2.10:1.03:2.09:1.89:3.79:4.13:1.82:1.83:3.90:2.39:2.09:2.94:1:00:1, which corresponds to the theoretical value, and successfully prepare 4' - (hexylmethacrylate oxy) -4- (oxyacetic acid anthracene-2-carbomethoxy) azobenzene.
Example 17
Synthesizing a monomer 4 '- (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN), and esterifying 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracene carbomethoxy) azobenzene and methacryloyl chloride at low temperature.
4' - (hydroxyhexyloxy) -4- (Anthranyloxy acetoacetate) azobenzene (0.74mmol, 0.42g) and triethylamine (1.0mmol, 0.1g) were dissolved in 10mL tetrahydrofuran to prepare a reaction solution, which was then placed in a round-bottomed flask. Methacryloyl chloride (0.74mmol, 0.07mL) was dissolved in 10mL of tetrahydrofuran and slowly dropped into the reaction solution through a constant pressure dropping funnel under an ice bath (0-5 ℃). After the reaction is finished for 5h, washing, drying, rotary evaporation and ethanol recrystallization are carried out, and the monomer 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) is obtained. As shown in FIG. 6, high performance liquid chromatography gave a purity of 96% with a yield of about 50%.
Example 18
Synthesizing a monomer 4 '- (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN), and esterifying 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracene carbomethoxy) azobenzene and methacryloyl chloride at low temperature.
4' - (hydroxyhexyloxy) -4- (Anthranyloxy acetoacetate) azobenzene (0.74mmol, 0.42g) and triethylamine (1.2mmol, 0.12g) were dissolved in 10mL tetrahydrofuran to prepare a reaction solution, which was then placed in a round-bottomed flask. Methacryloyl chloride (1.11mmol, 0.105mL) was dissolved in 10mL of tetrahydrofuran and slowly dropped into the reaction solution through a constant pressure dropping funnel under an ice bath (0-5 ℃). After the reaction is finished for 5h, washing, drying, rotary evaporation and ethanol recrystallization are carried out, and the monomer 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) is obtained. As shown in FIG. 6, high performance liquid chromatography gave a purity of 96% and a yield of about 62%.
Example 19
Synthesis of polymer poly 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (PMMA-AZO-AN).
Taking Azobisisobutyronitrile (AIBN) as AN initiator, N, N-Dimethylformamide (DMF) as a solvent, adding 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN, 0.63g and 1.0mmol) and AIBN (5mL) which are 1 percent of the mole number of the monomer into a polymerization bottle, freezing and vacuumizing by using liquid nitrogen, finally filling argon, and carrying out homopolymerization at 50 ℃. After the reaction is finished for 10h, dissolving with tetrahydrofuran, precipitating in ethanol for 3 times, and centrifuging by using a centrifugal tube to obtain homopolymer PMMA-AZO-AN.
FIG. 8 is a nuclear magnetic hydrogen spectrum of PMMA-AZO-AN. Chemical shifts δ 8.32ppm, 8.17ppm, 7.62ppm, 7.43ppm, 7.36ppm correspond to proton peaks (c-g) on the anthracene ring, chemical shifts δ 6.13ppm correspond to proton peaks (h) of the carbon attached to the anthracene ring, chemical shifts δ 4.44ppm correspond to proton peaks (i) of the carbon attached to the ester group, chemical shifts δ 7.84ppm, 7.73ppm, 6.83ppm, and 6.72ppm correspond to proton peaks (k, j) of the carbon above the azobenzene ring, chemical shifts 3.83ppm correspond to proton peaks (l) of the carbon attached to the oxygen element on the azobenzene, and chemical shifts δ 3.92ppm correspond to proton peaks (m) of the carbon attached to the oxygen element on the ester group. The ratio of each peak area obtained by integration is basically identical with the theoretical value, and the successful synthesis of the homopolymer PMMA-AZO-AN is proved.
FIG. 9 is a graph showing the molecular weight differential distribution of MMA-AZO-AN, which is a monomodal polymer having a single composition and AN integral giving a polymer having a number average molecular weight of 31800g/mol and a PDI of 1.86.
Example 20
Synthesis of polymer poly 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (PMMA-AZO-AN).
Taking Azobisisobutyronitrile (AIBN) as AN initiator and anisole as a solvent, taking 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN, 0.63g and 1.0mmol) as a monomer and AIBN (5mL) as AN initiator which is 1 percent of the mole number of the monomer into a polymerization bottle, freezing and vacuumizing liquid nitrogen, finally filling argon, and performing homopolymerization at 100 ℃. After the reaction is finished for 10h, dissolving with tetrahydrofuran, precipitating in ethanol for 3 times, and centrifuging by using a centrifugal tube to obtain homopolymer PMMA-AZO-AN.
Example 21
Synthesis of polymer poly 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (PMMA-AZO-AN).
Taking Azobisisobutyronitrile (AIBN) as AN initiator and tetrahydrofuran as a solvent, taking 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN, 0.63g and 1.0mmol) as a monomer and AIBN (5mL) as AN initiator which is 1 mol percent of the monomer, adding the initiator into a polymerization bottle, freezing by liquid nitrogen, vacuumizing, finally filling argon, and performing homopolymerization at 70 ℃. After the reaction is finished for 10h, dissolving with tetrahydrofuran, precipitating in ethanol for 3 times, and centrifuging by using a centrifugal tube to obtain homopolymer PMMA-AZO-AN.
Example 22
Synthesis of polymer poly 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (PMMAAZO-AN).
Taking Azobisisobutyronitrile (AIBN) as AN initiator and acetone as a solvent, taking 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN, 0.63g and 1.0mmol) as a monomer and AIBN (5mL) as AN initiator which is 1 mol percent of the monomer, adding the acetone into a polymerization bottle, freezing by liquid nitrogen, vacuumizing, finally filling argon, and performing homopolymerization at 60 ℃. After the reaction is finished for 10h, dissolving with tetrahydrofuran, precipitating in ethanol for 3 times, and centrifuging by using a centrifugal tube to obtain homopolymer PMMA-AZO-AN.
Example 23
Synthesis of polymer poly 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (PMMAAZO-AN).
Taking Azobisisobutyronitrile (AIBN) as AN initiator and toluene as a solvent, taking monomer 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN, 0.63g and 1.0mmol) as the initiator and AIBN as 1 mol percent of the monomer as the initiator, adding toluene (5mL) into a polymerization bottle, freezing by liquid nitrogen, vacuumizing, finally filling argon, and performing homopolymerization at 90 ℃. After the reaction is finished for 10h, dissolving with tetrahydrofuran, precipitating in ethanol for 3 times, and centrifuging by using a centrifugal tube to obtain homopolymer PMMA-AZO-AN.
Example 24
Synthesis of polymer poly 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (PMMA-AZO-AN).
Dibenzoyl peroxide (BPO) is used as AN initiator, anisole is used as a solvent, monomer 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN, 0.63g and 1.0mmol) is used as the initiator, the initiator BPO is 1 percent of the mole number of the monomer, anisole (5mL) is added into a polymerization bottle, liquid nitrogen is frozen and vacuumized, and finally argon is filled into the polymerization bottle to perform homopolymerization at 100 ℃. After the reaction is finished for 10h, dissolving with tetrahydrofuran, precipitating in ethanol for 3 times, and centrifuging by using a centrifugal tube to obtain homopolymer PMMA-AZO-AN.
Example 25
Synthesis of polymer poly 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (PMMA-AZO-AN).
Dibenzoyl peroxide (BPO) is used as AN initiator, toluene is used as a solvent, a monomer 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN, 0.63g and 1.0mmol) is used as the initiator, the initiator BPO is 1 mol percent of the monomer, the toluene (5mL) is added into a polymerization bottle, liquid nitrogen is frozen and vacuumized, and finally argon is filled into the polymerization bottle to perform homopolymerization at 90 ℃. After the reaction is finished for 10h, dissolving with tetrahydrofuran, precipitating in ethanol for 3 times, and centrifuging by using a centrifugal tube to obtain homopolymer PMMA-AZO-AN.
Example 25
The polymer PMMA-AZO-AN (0.1g) is dissolved in trichloromethane (5mL), the base material is a PET film, the PET film is coated on PET in a spinning mode to form a film, the film is placed in a blast oven at the temperature of 80 ℃ for 5 hours, the polymer film is scratched by a blade, the film is subjected to photo-repairing by ultraviolet light radiation for 10min, and the scratch disappears to show excellent photo-repairing performance.
Comparative example 1
Synthesis of polymer poly 4- (hexylmethacrylate oxy) azobenzene (PMMA-AZO).
Dibenzoyl peroxide (BPO) is used as an initiator, toluene is used as a solvent, a monomer 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO, 0.36g and 1.0mmol) is used as the initiator, the initiator BPO is 1 mol percent of the monomer, and the toluene (5mL) is added into a polymerization bottle, frozen by liquid nitrogen and vacuumized, and finally filled with argon gas to perform homopolymerization at 90 ℃. After the reaction is finished for 10h, dissolving with tetrahydrofuran, precipitating in ethanol for 3 times, and centrifuging by using a centrifugal tube to obtain the homopolymer PMMA-AZO.
The polymer PMMA-AZO (0.1g) is dissolved in trichloromethane (5mL), the base material is a PET film, the PET film is coated on PET in a spinning mode to form a film, the film is placed in a blowing oven at the temperature of 80 ℃ for 5 hours, a blade is used for scratching the polymer film, ultraviolet light is radiated on the film for 10 minutes to carry out light radiation, the scratches have no obvious change, and the control example shows that azobenzene and anthracene structures have a synergistic effect under the light radiation, so that the surface scratches can be repaired through light.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be obvious to those skilled in the art that modifications may be made in the technical solutions described in the above embodiments, or some technical features may be equivalently replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. The photorepairable azobenzene polymer PMMA-AZO-AN is characterized in that the structural general formula of the PMMA-AZO-AN is as follows:
Figure FDA0002820005170000011
in the formula: n is an integer, the molecular weight is 3000-100000, and PDI is 1.3-2.5.
2. The preparation method of the photorepairing azobenzene polymer PMMA-AZO-AN according to claim 1, characterized in that the steps of the preparation method are as follows:
(1) firstly, preparing 4-hydroxy hexyloxy azophenol; then, 2-bromoacetic acid anthracene-10-ylmethyl ester is prepared; finally, 4-hydroxy hexyloxy azophenol and 2-bromoacetic acid anthracene-10-methyl ester are substituted to prepare 4 '- (hydroxy hexyloxy) -4- (oxyacetic acid anthracene carbomethoxy) azobenzene, and then esterification reaction is carried out to prepare a monomer containing anthracene and azobenzene groups, 4' - (methyl acrylic acid hexyloxy) -4- (oxyacetic acid anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN);
(2) MMA-AZO-AN is used as a monomer, Azobisisobutyronitrile (AIBN) or dibenzoyl peroxide (BPO) is used as AN initiator, and free radical polymerization is carried out in the presence of a solvent to prepare poly 4' - (hexyl methacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (PMMA-AZO-AN).
3. The method for preparing the photorepairing azobenzene polymer PMMA-AZO-AN according to the claim 2, wherein the structural general formula of the 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) in the step (1) is as follows:
Figure FDA0002820005170000021
4. the method for preparing the photorepairing azobenzene polymer PMMA-AZO-AN according to claim 2, wherein the method for preparing the 4-hydroxyhexyloxyazophenol in the step (1) comprises the following steps:
(1) reacting 6-chlorohexanol and p-nitrophenol in the presence of inorganic base and using KI as a catalyst to prepare an intermediate p-nitrophenoxyhexanol, wherein the molar ratio of the 6-chlorohexanol to the p-nitrophenol is (0.5-2): 1, and the inorganic base is K2CO3Or Na2CO3The dosage of the compound is 1.24 times of the molar weight of the p-nitrophenol; the KI consumption is 0.08 percent of the mass of the p-nitrophenol, and the reaction conditions are as follows: refluxing DMF as solvent at 120 deg.C, reacting for 6 hr, and recrystallizing with ethanol to obtain intermediate;
(2) p-Nitrophenoxyhexanol in reducing agent Fe/NH4Reducing in the presence of Cl to prepare an intermediate p-aminophenoxy hexanol; wherein the dosage of the reducing agent Fe is 1-10 times of the molar weight of the p-nitrophenoxyhexanol, and Fe and NH4The mol ratio of Cl is 1 (1-3);
(3) diazotizing amino phenoxy hexanol under the action of an oxidant sodium nitrite, and performing coupling reaction with phenol to prepare an intermediate 4-hydroxy hexyloxy azophenol; the molar ratio of p-aminophenoxy hexanol to phenol is 1 (1-2), the use amount of sodium nitrite is 1-2 times of the molar amount of phenol, diazo coupling reaction is carried out at 0-5 ℃, and an intermediate is obtained through ethanol recrystallization and drying.
5. The method for preparing the photorepairing azobenzene polymer PMMA-AZO-AN according to claim 2, wherein the method for preparing the anthracene-10-ylmethyl 2-bromoacetate in the step (1) comprises the following steps: esterifying anthracene methanol and bromoacetyl bromide in the presence of an acid-binding agent at 0-5 ℃ to prepare an intermediate 2-bromoacetic acid anthracene-10-yl methyl ester; wherein, the molar ratio of the anthracene methanol to the bromoacetyl bromide is 1: (1-1.5) and triethylamine is used as an acid-binding agent, and the dosage of the acid-binding agent is 1-1.5 times of the molar weight of bromoacetyl bromide.
6. The method for preparing the photorepairing azobenzene polymer PMMA-AZO-AN according to claim 2, wherein the method for preparing the 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracenemethylcarbonyl) azobenzene in the step (1) comprises the following steps: 2-bromoacetic acid anthracene-10-methyl ester and 4-hydroxy hexyloxy azophenol are subjected to substitution reaction to prepare an intermediate 4' - (hydroxy hexyloxy) -4- (oxyacetic acid anthracene carbomethoxy) azobenzene; wherein the molar ratio of 2-bromoacetic acid anthracene-10-methyl ester to 4-hydroxy hexyloxy azophenol is (1-1.5): 1, the reaction condition is reflux reaction at 60 ℃ for 5h, and the product is prepared by ethanol recrystallization.
7. The method for preparing the photorepairing azobenzene polymer PMMA-AZO-AN according to the claim 2, wherein the method for preparing 4' - (hexylmethacrylate oxy) -4- (oxyacetic anthracene-2-carbomethoxy) azobenzene (MMA-AZO-AN) in the step (1) is as follows: 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracene carbomethoxy) azobenzene and methacryloyl chloride are esterified at low temperature to prepare the compound; wherein the mol ratio of 4' - (hydroxyhexyloxy) -4- (oxyacetic anthracenyl) azobenzene to methacryloyl chloride is 1: 1-1.5, slowly dripping methacryloyl chloride into the reaction solution through a constant-pressure dropping funnel under the esterification reaction condition of 0-5 ℃, and recrystallizing with ethanol after 5 hours.
8. The method for preparing the photorepairing azobenzene polymer PMMA-AZO-AN according to claim 2, characterized in that the solvent in the step (2) is Tetrahydrofuran (THF), N-dimethylformamide, acetone, anisole and toluene, and the polymerization temperature is 50-100 ℃; AIBN or BPO is used in an amount of 1 mol% based on the monomer.
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