CN108484832B - Preparation method of self-healing hydrogel with ultraviolet and pH sensitivity - Google Patents

Preparation method of self-healing hydrogel with ultraviolet and pH sensitivity Download PDF

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CN108484832B
CN108484832B CN201810342852.7A CN201810342852A CN108484832B CN 108484832 B CN108484832 B CN 108484832B CN 201810342852 A CN201810342852 A CN 201810342852A CN 108484832 B CN108484832 B CN 108484832B
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CN108484832A (en
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贾鹏翔
杨萌
程永斌
马可
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Northwestern University
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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Abstract

A preparation method of self-healing hydrogel with ultraviolet and pH sensitivity comprises the following steps: step 1, preparing an azobenzene polymerizable monomer, and forming a host-guest inclusion compound by using cyclodextrin and the azobenzene polymerizable monomer; step 2, preparing a phenylboronic acid polymerizable monomer; step 3, reacting a phenylboronic acid polymerizable monomer with cis-diol on the cyclodextrin inclusion compound under an alkaline condition to form a crosslinking point, separating liquid by using a separating funnel, wherein the yellow emulsion at the lowermost layer is the formed azobenzene cyclodextrin inclusion compound; step 4, adding a redox initiator, a cross-linking agent and a water-soluble monomer at room temperature to obtain hydrogel with ultraviolet and pH responsiveness and self-healing performance; adopts simple synthesis steps, depends on a physical non-covalent host-guest package and action and a chemical covalent reversible boric acid ester bond, and forms the hydrogel with self-healing function, pH sensitivity, strong mechanical property and stability.

Description

Preparation method of self-healing hydrogel with ultraviolet and pH sensitivity
Technical Field
The invention belongs to the technical field of hydrogel preparation, and particularly relates to a method for quickly preparing ultraviolet and pH sensitive self-healing hydrogel. The gel with ultraviolet and pH dual responsiveness and self-healing water performance is obtained by specifically applying cyclodextrin and an azobenzene monomer to form a host-guest inclusion effect, forming a cross-linking point with a boric acid group on a phenylboronic acid polymerizable monomer through cis-diol on the cyclodextrin under an alkaline condition, and then adding a water-soluble monomer and an initiator to perform polymerization.
Background
A gel is a polymer or macromolecular aggregate that absorbs a large amount of solvent but is insoluble in the solvent, and it is called a soft material because it rapidly swells and equilibrates in water and maintains its shape and three-dimensional spatial network structure. Hydrogels are ubiquitous in natural systems, particularly in living organisms, and are a hydrophilic polymeric network and are capable of absorbing large amounts of water. The hydrogel is widely applied to the fields of wound dressings, biological tissue engineering, drug delivery systems, human medical devices and the like. The gel implanted into organism is damaged due to the fact that the gel is easily squeezed by external force, body fluid is corroded, and other chemical substances are invaded, so that cracks appear in the gel to influence the integrity and the mechanical property of the gel structure, the service life of the gel implant is further shortened, the health and the safety of a patient are critical, but the damaged gel is difficult to repair and clean manually. The proposal of the self-healing hydrogel provides a possible way for repairing the micro-cracks of the soft material, prolonging the service life of the gel material and improving the safety of the gel material.
The self-healing hydrogel mainly utilizes the principle of dynamic construction chemistry, which is proposed by parent Lehn of supermolecule, and based on the principle, the design and repair modes of the self-healing hydrogel can be summarized and generalized into two types: one type is a physical self-healing hydrogel based on weak interaction force in supermolecular chemistry, mainly depends on intermolecular forces such as hydrophobic interaction, hydrogen bond, electrostatic attraction, crystallization and the like to form a reversible gel network system, has the advantages that crosslinking has transient characteristics, can relax stress through the damage and reformation of crosslinking points, and has the defects that the intermolecular forces of the gels formed through the interaction are weak and the stability is not high; the other type is a chemical self-healing hydrogel based on dynamic covalent chemistry, and the special covalent bonds have the stable property of covalent bonds and certain reversibility and provide conditions for the self-healing of the gel. Cyclodextrins are cyclic oligomers linked by glycosidic bonds and have their own molecular structure: the amphiphilic characteristics of intracavity hydrophobicity and extraluminal hydrophilicity can be combined with hydrophobic guest molecules with selectivity and size and shape matched with cavities of the hydrophobic guest molecules to generate interaction, a complex is formed in an aqueous phase medium, and the interaction between the host and the guest is widely used for preparing self-healing hydrogel. In addition, the cis-diol on the cyclodextrin can also form a reversible covalent bond with phenylboronic acid. According to the invention, host-guest interaction and borate reversible chemical bonds are simultaneously introduced into the hydrogel through cyclodextrin, so that the self-healing hydrogel with ultraviolet and pH dual responsiveness is obtained, and no relevant literature report exists at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing a self-healing hydrogel with ultraviolet and pH dual responsiveness, so as to overcome the defects of complex synthesis steps, low self-healing efficiency, poor biocompatibility and the like of the self-healing hydrogel in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of self-healing hydrogel with ultraviolet and pH sensitivity comprises the following steps:
step 1, preparing an azobenzene polymerizable monomer, and forming a host-guest inclusion compound by using cyclodextrin and the azobenzene polymerizable monomer;
step 2, preparing phenylboronic acid polymerizable monomers, putting 1.50-1.70 g of 3-aminophenylboronic acid monohydrate into a 150mL three-necked flask, dissolving the phenylboronic acid polymerizable monomers with an alkali solution, adding 30 mL-70 mL of distilled water, stirring, adjusting pH to be 4.6-4.9 with an acid, adding EDC when introducing nitrogen at 0-6 ℃, taking methacrylic acid or acrylic acid with a molar weight of 0.5-1.5 times that of the phenylboronic acid, diluting with 2 mL-20 mL of water, adjusting pH to be 4.6-4.9, gradually adding the mixture into the phenylboronic acid solution, reacting for 0.8-3 h, extracting with 30 mL-80 mL of diethyl ether for 1-4 times to obtain an organic phase, filtering powdery solids in the organic phase, removing the diethyl ether with a rotary evaporator, drying in a vacuum drying oven at 30-60 ℃ overnight to obtain a light yellow solid, and adopting the volume ratio of ethanol water: ethanol: recrystallizing the mixed solution with water =10: 90-30: 70 at 35-60 ℃ to obtain a product;
step 3, reacting a phenylboronic acid polymerizable monomer with cis-diol on the cyclodextrin inclusion compound to form a crosslinking point under the alkaline condition that the pH value is more than or equal to 9, separating liquid by using a separating funnel, wherein the yellow emulsion at the lowermost layer is the formed azobenzene cyclodextrin inclusion compound;
and 4, adding a redox initiator with the molar weight of 0.5-3.0% of that of the acrylamide monomer, 1-3 mg of a cross-linking agent and 1-3 g of a water-soluble monomer at room temperature, and obtaining the hydrogel with ultraviolet and pH responsiveness and self-healing performance after 5-20 minutes, wherein the hydrogel is of a 3D network structure.
A preparation method of self-healing hydrogel with ultraviolet and pH sensitivity comprises the following steps:
step 1, preparing an azobenzene polymerizable monomer: adding 5.70-6.10 g of p-aminoazobenzene monomer into a round-bottom flask, stirring and dissolving by 10-40 mL of toluene, sequentially adding 4.0-4.5 mL of triethylamine and 30-50 mg of hydroquinone, dropwise adding methacryloyl chloride or acryloyl chloride with the molar weight of azobenzene of 0.8-1.5 times at room temperature while stirring until orange-red solid appears, stirring and refluxing for three hours at 55-70 ℃, cooling after reaction, performing suction filtration, performing vacuum drying at 55-70 ℃ to remove toluene, washing the obtained orange-red solid with a small amount of distilled water, performing suction filtration, performing vacuum drying at 45-55 ℃ to remove water, recrystallizing for 1-3 times in absolute ethyl alcohol to obtain orange-red crystals, and performing vacuum drying;
step 2, preparing phenylboronic acid polymerizable monomer: accurately weighing 1.50-1.70 g of 3-aminophenylboronic acid monohydrate in a 150mL three-necked flask, dissolving the 3-aminophenylboronic acid monohydrate by using an alkali solution, adding 30-70 mL of distilled water for stirring, adjusting the pH to be = 4.6-4.9 by using an acid, adding EDC when introducing nitrogen at 0-6 ℃, taking methacrylic acid or acrylic acid with the molar weight of 0.5-1.5 times of that of the phenylboronic acid, diluting and adjusting the pH to be = 4.6-4.9 by using 2-20 mL of water, gradually adding the solution into the phenylboronic acid solution for reacting for 0.8-3 h, extracting for 1-4 times by using 30-80 mL of diethyl ether to obtain an organic phase, filtering powdery solid in the organic phase, removing the diethyl ether by using a rotary evaporator, drying in a vacuum drying oven at 30-60 ℃ overnight to obtain a light yellow solid, and adopting the volume ratio of ethanol water: ethanol: recrystallizing the mixed solution with water =10: 90-30: 70 at 35-60 ℃ to obtain a product;
step 3, forming a water solution by cyclodextrin and distilled water at room temperature, mixing and stirring the water solution and the toluene solution of the azobenzene monomer obtained in the step 1 for 12-24 hours according to the molar ratio of 1: 3-3: 1, and separating the solution by using a separating funnel, wherein the yellow emulsion at the lowest layer is the formed azobenzene cyclodextrin inclusion compound; the cyclodextrin is one or more of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin;
and 4, putting 10-50 mg of phenylboronic acid polymerizable monomer into a beaker, dissolving the phenylboronic acid polymerizable monomer with a sodium hydroxide solution, adding 7.5-9.5 mL of distilled water, adding 1-5 mL of the emulsion obtained in the step 3, stirring the mixture at room temperature for 3-5 h, adding a redox initiator with the molar weight being 0.5-3.0% of that of the acrylamide monomer, 1-3 mg of a cross-linking agent and 1-3 g of a water-soluble monomer, uniformly stirring the mixture, and standing the mixture for reaction at 20-40 ℃ for 5-20 minutes to obtain the hydrogel.
The mass volume ratio of the cyclodextrin to the distilled water in the step 3 is 1:50 g/mL-1: 200g/mL, and the mass volume ratio of the azobenzene monomer to the toluene is 0.2:10 g/mL-0.2: 200 g/mL.
The concentration of the phenylboronic acid polymerizable monomer in the step 4 is 0.16 g/mL-0.6 g/mL.
The concentration of the emulsion in the step 4 is 0.0083 g/mL-0.05 g/mL.
The concentration of the water-soluble monomer in the step 4 is 0.025 g/mL-0.3 g/mL; the hydrophilic monomer is one or more of acrylic acid, methacrylic acid, acrylamide, methacrylamide and hydroxyethyl methacrylate.
The redox initiator in the step 4 is potassium persulfate and tetramethylethylenediamine, and the molar ratio of the potassium persulfate to the tetramethylethylenediamine is 1: 1.
The redox system in the step 4 is potassium persulfate and tetramethylethylenediamine, and the dosage of the redox system is 0.5-2.5% of the water-soluble monomer.
The cross-linking agent in the step 4 is one or more of ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate (200) and N, N-methylene bisacrylamide, and the dosage of the cross-linking agent is 0.03-0.1% of the dosage of the water-soluble monomer substance.
The invention has the beneficial effects that:
compared with the prior art, the invention has the advantages of integrating the advantages of the two, adopting simple synthesis steps, and forming the hydrogel with self-healing function, pH sensitivity, strong mechanical property and stability by means of the interaction of host-guest inclusion belonging to physical non-covalent type and dynamic borate belonging to chemical dynamic covalent bond type.
The hydrogel is prepared by forming a host-guest inclusion compound from cyclodextrin and an azobenzene polymerizable monomer, then adding a phenylboronic acid polymerizable monomer into the emulsion under an alkaline condition, reacting for a certain time, and then adding a redox initiation system, a water-soluble monomer and a proper amount of a cross-linking agent at room temperature to prepare the gel. If the crosslinking agent is not added, the formed gel is opaque and has poor moldability, but can be self-healed immediately. The addition of a proper amount of cross-linking agent can prepare an ideal shape, and the tensile property and the self-healing efficiency can be well characterized. The mechanical property and the self-healing efficiency of the gel can be adjusted by changing the content of the emulsion, the content of the cross-linking agent and the amount of the phenylboronic acid polymerizable monomer. According to the three variables, the hydrogel with good mechanical property, high self-healing efficiency and good pH response can be obtained by designing an orthogonal test for experiment.
The hydrogel of the invention has the following properties: at room temperature, the self-healing can be realized without any external action, and the self-healing efficiency is up to more than 90%; the composite material has good mechanical property, the elongation at break can reach 800%, the breaking stress is 40kpa, and the composite material can still return according to the original route after being stretched for 8 times without intermission and circulation; has ultraviolet light responsiveness and reversibility under ultraviolet-visible light; has obvious pH sensitivity; has plasticity and can be made into any shape.
Drawings
Fig. 1(a) is a tensile test chart of the self-healing hydrogel with uv and pH sensitivity prepared in example 1 of the present invention.
Fig. 1(b) is a tensile test chart of the self-healing hydrogel with uv and pH sensitivity prepared in example 2 of the present invention.
Fig. 2(a) is a uv-vis spectrum of the self-healing hydrogel with uv and pH sensitivity prepared in example 1 of the present invention.
Fig. 2(b) is a uv-vis spectrum of the self-healing hydrogel with uv and pH sensitivity prepared in example 2 of the present invention.
Fig. 3 is a graph of swelling ratios at different pH values for a uv-pH sensitive self-healing hydrogel prepared in examples 1 and 2, where the straight line is the swelling ratio at different pH values for a uv-pH sensitive self-healing hydrogel prepared in example 1, and the dotted line is the swelling ratio at different pH values for a uv-pH sensitive self-healing hydrogel prepared in example 2.
Fig. 4(a) is a cyclic tensile test chart of the self-healing hydrogel with uv and pH sensitivity prepared in example 1 of the present invention.
Fig. 4(b) is a cyclic tensile test chart of the self-healing hydrogel with uv and pH sensitivity prepared in example 2 of the present invention.
Fig. 5(a) is a photograph of the self-healing hydrogel with uv, pH sensitivity prepared in example 1 of the present invention before stretching after self-healing.
Fig. 5(b) is a photograph after stretching after self-healing of the self-healing hydrogel having uv and pH sensitivity prepared in example 1 of the present invention.
Fig. 6(a) is a photograph of the self-healing hydrogel with uv, pH sensitivity prepared in example 2 of the present invention before stretching after self-healing.
Fig. 6(b) is a photograph after stretching after self-healing of the self-healing hydrogel with uv, pH sensitivity prepared in example 2 of the present invention.
Detailed Description
The production method of the present invention will be described in detail with reference to examples.
Example 1
A preparation method of self-healing hydrogel with ultraviolet and pH sensitivity comprises the following steps:
step 1, preparing an azobenzene polymerizable monomer: adding 5.70g of p-aminoazobenzene monomer into a round-bottom flask, stirring and dissolving the p-aminoazobenzene monomer by using 10mL of methylbenzene, sequentially adding 4.0mL of triethylamine and 30mg of hydroquinone, dropwise adding methacryloyl chloride or acryloyl chloride with the molar weight of azobenzene being 0.8 time at room temperature while stirring until an orange-red solid appears, stirring and refluxing the mixture at 55 ℃ for three hours to react, cooling the reaction product after the reaction is finished, performing suction filtration, performing vacuum drying at 55 ℃ to remove methylbenzene, washing the obtained orange-red solid by using a small amount of distilled water, performing suction filtration, performing vacuum drying at 45 ℃ to remove water, recrystallizing the obtained orange-red solid in absolute ethyl alcohol for 1 time to obtain an orange;
step 2, preparing phenylboronic acid polymerizable monomers, accurately weighing 1.50g of 3-aminophenylboronic acid monohydrate into a 150mL three-necked flask, dissolving the 3-aminophenylboronic acid monohydrate with an alkali solution, adding 30mL of distilled water, stirring, adjusting the pH to be =4.6 with an acid, adding EDC when introducing nitrogen at 0 ℃, diluting methacrylic acid or acrylic acid with the molar weight of 0.5 times of that of the phenylboronic acid with 2mL of water, adjusting the pH to be =4.6, gradually adding the methacrylic acid or the acrylic acid into the phenylboronic acid solution, reacting for 0.8h, extracting with 30mL of diethyl ether for 2 times to obtain an organic phase, filtering powdery solids in the organic phase, removing the diethyl ether with a rotary evaporator, drying at 30 ℃ in a vacuum drying oven for one night to obtain a pale yellow solid, and adopting the volume ratio of ethanol water: ethanol: recrystallizing the mixed solution of water =10:90 at 35 ℃ to obtain a product;
step 3, mixing and stirring the aqueous solution of cyclodextrin and the toluene solution of azobenzene polymerizable monomer for 12 hours according to the molar ratio of 1:3, and layering by using a separating funnel, wherein the emulsion at the bottommost layer is a host-guest inclusion compound;
and 4, adding 1mL of emulsion into an alkaline aqueous solution containing 40mg of phenylboronic acid polymerizable monomer, adding distilled water to 10mL, reacting for 3 hours, adding 3g of acrylamide, potassium persulfate and tetramethylethylenediamine which account for 0.5% of water-soluble monomers and 1mg of N, N-methylene bisacrylamide, uniformly stirring, putting into a mold, and forming gel at room temperature for 5 minutes.
The hydrogel in a stick shape was subjected to a tensile test using a universal electronic tester, and as shown in FIG. 1(a), a hydrogel formed with 1mg of a crosslinking agent, 1mL of an emulsion, and 40mg of a phenylboronic acid polymerizable monomer among all the gels formed could be stretched to 400% of the original length. The self-healing time is 24 hours at room temperature, and the self-healing efficiency can reach 100 percent. As shown in FIG. 2(a), the characteristic peaks of the hydrogel at 438nm and 354nm were found to change before and after UV irradiation due to cis-trans isomeric changes of azobenzene. As shown in fig. 3, the swelling ratio of the hydrogel greatly differs in solutions with different pH values for 4 days, because under alkaline conditions (pH = 11), cis-diol and borate can form stable borate ions, the electrostatic repulsion between intermolecular borate ions makes the polymer chain more stretched, and the borate ions have hydrophilicity, thereby facilitating the entry of water molecules in the solution, i.e., showing the tendency that the swelling ratio of the hydrogel increases with the increase of the environmental pH value. As shown in fig. 4(a), the tensile stress-strain curve of the sample can still return according to the original route without intermittent cyclic stretching for 8 times, which indicates that the prepared hydrogel has better mechanical recovery performance. As shown in FIG. 5(a), the length of the gel which starts to self-heal immediately after cutting is 5cm, and as shown in FIG. 5(b), the gel can stretch to 31cm after self-healing for 12h, which proves that the hydrogel prepared has good self-healing performance.
Example 2
A preparation method of self-healing hydrogel with ultraviolet and pH sensitivity comprises the following steps:
step 1, preparing an azobenzene polymerizable monomer: adding 6.00g of p-aminoazobenzene monomer into a round-bottom flask, stirring and dissolving the p-aminoazobenzene monomer by using 20mL of toluene, sequentially adding 4.2mL of triethylamine and 40mg of hydroquinone, dropwise adding methacryloyl chloride or acryloyl chloride with the molar weight 1.1 times of that of azobenzene at room temperature while stirring until an orange-red solid appears, stirring and refluxing the mixture at 65 ℃ for three hours to react, cooling the reaction product after the reaction is finished, performing suction filtration, performing vacuum drying at 65 ℃ to remove the toluene, washing the obtained orange-red solid by using a small amount of distilled water, performing suction filtration, performing vacuum drying at 50 ℃ to remove water, recrystallizing the obtained orange-red solid in absolute ethyl alcohol for 2 times to obtain an orange;
step 2, preparing phenylboronic acid polymerizable monomer: accurately weighing 1.60g of 3-aminophenylboronic acid monohydrate in a 150mL three-necked flask, dissolving the 3-aminophenylboronic acid monohydrate by using an alkali solution, adding 50mL of distilled water for stirring, adjusting the pH to be =4.7 by using an acid, adding EDC (the Chinese name is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) when introducing nitrogen at 4 ℃, diluting methacrylic acid or acrylic acid with the molar weight of the phenylboronic acid being 1.0 time so that the pH is =4.7 by using 8mL of water for gradually adding the mixture into the phenylboronic acid solution for reaction for 2 hours, extracting the mixture for 3 times by using 50mL of diethyl ether to obtain an organic phase, filtering powdery solid in the organic phase, removing the diethyl ether by using a rotary evaporator, drying the mixture overnight at 45 ℃ in a vacuum drying oven to obtain a pale yellow solid, and using the volume ratio of ethanol water: ethanol: recrystallizing the mixed solution of water =20:80 at 50 ℃ to obtain a product;
step 3, mixing and stirring the cyclodextrin water solution and the toluene solution of the azobenzene polymerizable monomer for 18 hours at room temperature according to the molar ratio of 1:1, and layering by using a separating funnel, wherein the emulsion at the bottommost layer is a host-guest inclusion compound;
and 4, adding 5mL of emulsion into an alkaline aqueous solution containing 30mg of phenylboronic acid polymerizable monomer, adding distilled water to 11mL, reacting for 4 hours, adding 2g of acrylamide, potassium persulfate and tetramethylethylenediamine which account for 1.0% of water-soluble monomers and 1mg of N, N-methylene bisacrylamide, uniformly stirring, putting into a mold, and forming gel at room temperature for 13 minutes.
The hydrogel in a stick shape was subjected to a tensile test using a universal electronic tester, and as shown in FIG. 1(b), a hydrogel formed in which the amount of the crosslinking agent was 1mg of the emulsion was 30mg of the phenylboronic acid polymerizable monomer in 5mL of the total gel formed could be stretched to 820% of the original length. The self-healing time is 24 hours at room temperature, and the self-healing efficiency can reach more than 95%. As shown in FIG. 2(b), the peak change of the hydrogel at 354nm and 438nm was found to be significant as a result of the UV-visible spectrum, since the concentration of the cis-trans-isoazobenzene was high, the peak change before and after UV irradiation and after visible irradiation was clearly seen. As shown in fig. 3, the swelling ratio of the hydrogel greatly differs in solutions with different pH values for 4 days, because under alkaline conditions (pH = 11), cis-diol and borate can form stable borate ions, the electrostatic repulsion between intermolecular borate ions makes the polymer chain more stretched, and the borate ions have hydrophilicity, thereby facilitating the entry of water molecules in the solution, i.e., showing the tendency that the swelling ratio of the hydrogel increases with the increase of the environmental pH value. However, the swelling ratio of the hydrogel formed with 30mg of the phenylboronic acid polymerizable monomer having 1mg of the emulsion as the crosslinking agent was relatively decreased compared with the swelling ratio of the hydrogel formed with 40mg of the phenylboronic acid polymerizable monomer having 1mL of the emulsion as the crosslinking agent under the same conditions, because the content of the emulsion of the hydrogel formed with 30mg of the phenylboronic acid polymerizable monomer having 1mg of the emulsion as the crosslinking agent was much higher than that of the hydrogel formed with 40mg of the phenylboronic acid polymerizable monomer having 1mg of the emulsion as the crosslinking agent in 10mL of the same solution, although the content of the phenylboronic acid in the hydrogel formed with 40mg of the phenylboronic acid polymerizable monomer having 1mg of the emulsion as the crosslinking agent was slightly higher than that of the hydrogel formed with 30mg of the phenylboronic acid polymerizable monomer having 1mg of the emulsion as the crosslinking agent in 5mL of the phenylboronic acid polymerizable monomer, from 30mg of the phenylboronic acid polymerizable monomer having 1mg of the emulsion as the crosslinking agent in total, from the viewpoint of the whole The hydrogel formed by 40mg of phenylboronic acid polymerizable monomer with 1mg of emulsion as 1mL has a high degree of crosslinking and a small effective chain average molecular weight, so the swelling degree is small. As shown in fig. 4(b), the tensile stress-strain curve of the sample can still return according to the original route without intermittent cyclic stretching for 7 times, which indicates that the prepared hydrogel has better mechanical recovery performance. As shown in FIG. 6(a), the length of the gel which starts to self-heal immediately after cutting is 5.5cm, and as shown in FIG. 6(b), the gel can stretch to 20cm after self-healing for 12h, which proves that the prepared hydrogel has good self-healing performance.
Example 3
A preparation method of self-healing hydrogel with ultraviolet and pH sensitivity comprises the following steps:
step 1, preparing an azobenzene polymerizable monomer: adding 6.10g of p-aminoazobenzene monomer into a round-bottom flask, stirring and dissolving the p-aminoazobenzene monomer by using 40mL of toluene, sequentially adding 4.5mL of triethylamine and 50mg of hydroquinone, dropwise adding methacryloyl chloride or acryloyl chloride with the molar weight 1.5 times of that of azobenzene at room temperature while stirring until an orange-red solid appears, stirring and refluxing the mixture at 70 ℃ for three hours to react, cooling the reaction product after the reaction is finished, performing suction filtration, performing vacuum drying at 70 ℃ to remove the toluene, washing the obtained orange-red solid by using a small amount of distilled water, performing suction filtration, performing vacuum drying at 55 ℃ to remove water, recrystallizing the obtained orange-red solid in absolute ethyl alcohol for 3 times to obtain an orange;
step 2, preparing phenylboronic acid polymerizable monomer: accurately weighing 1.70g of 3-aminophenylboronic acid monohydrate in a 150mL three-necked flask, dissolving the 3-aminophenylboronic acid monohydrate by using an alkali solution, adding 70mL of distilled water for stirring, adjusting the pH to be =4.9 by using an acid, adding EDC when introducing nitrogen at 6 ℃, diluting methacrylic acid or acrylic acid with the molar weight being 1.5 times that of the phenylboronic acid by using 20mL of water to adjust the pH to be =4.9, gradually adding the mixture into the phenylboronic acid solution for reacting for 3h, extracting the mixture for 4 times by using 80mL of diethyl ether to obtain an organic phase, filtering powdery solid in the organic phase, removing the diethyl ether by using a rotary evaporator, drying the mixture at 60 ℃ in a vacuum drying oven for one night to obtain a light yellow solid, and using the volume ratio of ethanol water: ethanol: recrystallizing the mixed solution of water =30:70 at 60 ℃ to obtain a product;
step 3, mixing and stirring the cyclodextrin aqueous solution and a toluene solution of an azobenzene polymerizable monomer for 24 hours at room temperature according to the molar ratio of 3:1, and layering by using a separating funnel, wherein the emulsion at the bottommost layer is a host-guest inclusion compound;
and 4, adding 5mL of emulsion into an alkaline aqueous solution containing 40mg of phenylboronic acid polymerizable monomer, adding distilled water to 12mL, reacting for 5 hours, adding 3g of acrylamide, potassium persulfate and tetramethylethylenediamine which account for 3.0% of water-soluble monomers and 3mg of N, N-methylene bisacrylamide, uniformly stirring, putting into a mold, and forming gel at room temperature for 20 minutes.
The hydrogel with good self-healing performance, ultraviolet response, pH response and mechanical property is prepared for the first time, and the multifunctional hydrogel has good application prospect in the fields of biomedicine and engineering.

Claims (6)

1. A preparation method of self-healing hydrogel with ultraviolet and pH sensitivity is characterized by comprising the following steps:
step 1, preparing an azobenzene polymerizable monomer: adding 5.70-6.10 g of p-aminoazobenzene monomer into a round-bottom flask, stirring and dissolving by 10-40 mL of toluene, sequentially adding 4.0-4.5 mL of triethylamine and 30-50 mg of hydroquinone, dropwise adding methacryloyl chloride or acryloyl chloride with the molar weight of azobenzene of 0.8-1.5 times at room temperature while stirring until orange-red solid appears, stirring and refluxing for three hours at 55-70 ℃, cooling after reaction, performing suction filtration, performing vacuum drying at 55-70 ℃ to remove toluene, washing the obtained orange-red solid with a small amount of distilled water, performing suction filtration, performing vacuum drying at 45-55 ℃ to remove water, recrystallizing for 1-3 times in absolute ethyl alcohol to obtain orange-red crystals, and performing vacuum drying;
step 2, preparing phenylboronic acid polymerizable monomer: accurately weighing 1.50-1.70 g of 3-aminophenylboronic acid monohydrate in a 150mL three-necked flask, dissolving the 3-aminophenylboronic acid monohydrate by using an alkali solution, adding 30-70 mL of distilled water for stirring, adjusting the pH to be = 4.6-4.9 by using an acid, adding EDC when introducing nitrogen at 0-6 ℃, taking methacrylic acid or acrylic acid with the molar weight of 0.5-1.5 times of that of the phenylboronic acid, diluting and adjusting the pH to be = 4.6-4.9 by using 2-20 mL of water, gradually adding the solution into the phenylboronic acid solution for reacting for 0.8-3 h, extracting for 1-4 times by using 30-80 mL of diethyl ether to obtain an organic phase, filtering powdery solid in the organic phase, removing the diethyl ether by using a rotary evaporator, drying in a vacuum drying oven at 30-60 ℃ overnight to obtain a light yellow solid, and adopting the volume ratio of ethanol water: ethanol: recrystallizing the mixed solution with water =10: 90-30: 70 at 35-60 ℃ to obtain a product;
step 3, forming a water solution by cyclodextrin and distilled water at room temperature, mixing and stirring the water solution and the toluene solution of the azobenzene monomer obtained in the step 1 for 12-24 hours according to the molar ratio of 1: 3-3: 1, and separating the solution by using a separating funnel, wherein the yellow emulsion at the lowest layer is the formed azobenzene cyclodextrin inclusion compound; the cyclodextrin is one or more of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin;
and 4, putting 10-50 mg of phenylboronic acid polymerizable monomer into a beaker, dissolving the phenylboronic acid polymerizable monomer with a sodium hydroxide solution, adding 7.5-9.5 mL of distilled water, adding 1-5 mL of the emulsion obtained in the step 3, stirring the mixture at room temperature for 3-5 h, adding a redox initiator with the molar weight being 0.5-3.0% of the molar weight of the water-soluble monomer, 1-3 mg of a cross-linking agent and 1-3 g of the water-soluble monomer, uniformly stirring the mixture, and standing the mixture for reaction at 20-40 ℃ for 5-20 minutes to obtain the hydrogel.
2. The method for preparing a self-healing hydrogel with ultraviolet and pH sensitivity according to claim 1, wherein the mass-to-volume ratio of cyclodextrin to distilled water in step 3 is 1:50 g/mL-1: 200g/mL, and the mass-to-volume ratio of azobenzene monomer to toluene is 0.2:10 g/mL-0.2: 200 g/mL.
3. The method for preparing a self-healing hydrogel with uv and pH sensitivity according to claim 1, wherein the water-soluble monomer is one or more of acrylic acid, methacrylic acid, acrylamide, methacrylamide, and hydroxyethyl methacrylate.
4. The method for preparing a self-healing hydrogel with uv and pH sensitivity according to claim 1, wherein the redox initiator in step 4 is potassium persulfate and tetramethylethylenediamine with a molar ratio of 1: 1.
5. A method for preparing a self-healing hydrogel with uv and pH sensitivity according to claim 1, wherein the redox initiator in step 4 is potassium persulfate and tetramethylethylenediamine, which is used in an amount of 0.5% to 2.5% of the amount of the water-soluble monomer material.
6. A method for preparing a self-healing hydrogel with uv and pH sensitivity according to claim 1, wherein the cross-linking agent in step 4 is one or more of ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate (200), and N, N-methylenebisacrylamide, and the amount thereof is 0.03% to 0.1% of the amount of the water-soluble monomer material.
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