CN105713134B - A kind of magnetic field based on acylhydrazone key dynamic reversible selfreparing, the preparation method of the double response type intelligent aqueous gels of temperature - Google Patents

Abstract

The invention relates to a method for preparing a magnetic field and temperature dual-response intelligent hydrogel based on the dynamic reversible self-repair of an acylhydrazone bond, that is, the product pentaerythritol bromide obtained by brominating pentaerythritol is used as an initiator to trigger diethylene glycol monomethyl Atom transfer radical polymerization of ether methacrylate and methacrylate oligopolyethylene glycol ester monomers, the obtained random copolymer is further azide; Utilize p-hydroxybenzaldehyde and propargyl bromide to prepare p-propargyl oxybenzaldehyde. The two-step product was obtained through a copper-catalyzed azide-alkyne cycloaddition reaction to form an aldylated polymer. Ferroferric oxide magnetic nanoparticles were prepared by co-precipitation method and modified by amination. A temperature-responsive hydrogel with self-healing properties was prepared by utilizing the dynamically reversible acylhydrazone bonds formed between the aldehyde groups on the polymer and the primary amines on the magnetic particles. Under normal temperature and neutral conditions, the gel fragments can be attracted and aggregated by a magnetic field, and repaired through the formation of acylhydrazone bonds to restore the gel as a whole. The preparation method of the invention has high feasibility, easy-to-obtain raw materials, and good development and popularization.

Description

A dynamic and reversible self-healing smart device based on acylhydrazone bonds Preparation method of hydrogel

technical field

The invention belongs to the field of polymer materials, and in particular relates to a method for preparing a magnetic field and temperature dual-response intelligent hydrogel based on acylhydrazone bond dynamic reversible self-repair.

Background technique

The traditional method of improving the service life of materials is generally to directly improve the durability, mechanical properties and other properties of materials, rather than considering the self-healing characteristics of materials. Self-healing materials, as a new force in emerging materials, as the name suggests, can spontaneously repair the damage when the material is damaged by external impacts such as cracks, and keep the properties of the material basically at the original level, which is very important for improving the service life of the material. And performance has important application value. Usually, fracture toughness, tensile properties, fracture deformation rate, etc. are used as indicators for evaluating the degree of recovery of materials. During the repair process of the material, the two fractured interfaces are automatically bonded together by physical or chemical methods. At the macroscopic level, there is no obvious connection trace. No secondary damage occurs to prove that the original fracture interface has been well repaired. The mechanism of material self-healing is different, and the dynamic reverse combination of reversible covalent bond or non-covalent bond can be used to achieve fracture healing. The bond energy of the reversible covalent bond is larger than that of the non-covalent bond, and the bond strength is stronger, which ensures the performance of the repaired material.

Hydrogel is formed by a large amount of water solvent and a small amount of polymer three-dimensional network components through covalent bonds or intermolecular forces, and has a wide range of applications in the fields of daily food, electronic processing, drug sustained release, and tissue engineering. application potential. Using dynamic covalent bonds to form cross-linking points to prepare smart hydrogels with self-healing properties, in addition to endowing hydrogels with temperature, magnetic or pH, light and other responsiveness, will greatly increase the application value of the gel.

Utilizing the dynamic acylhydrazone bond formed between the primary amine on the modified magnetic nanoparticles and the aldehyde group on the end of the temperature-responsive polymer, its splitting and recombination can continue to occur in the hydrogel network and maintain a dynamic balance, so It can restore its own system without external stimuli.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a magnetic field and temperature double-responsive intelligent hydrogel based on the dynamic reversible self-repair of the acylhydrazone bond.

The purpose of the present invention is to combine the aminated magnetic nanoparticles with the alkynylated temperature-sensitive polymer to prepare a hydrogel by establishing a dynamically reversible acylhydrazone bond. The invention prepares ferroferric oxide magnetic nanoparticles through a co-precipitation method, and performs amination modification on them. The product after the bromination of pentaerythritol with commercialization is initiator, initiates the random copolymerization of commercialized diethylene glycol monomethyl ether methacrylate and methacrylate oligomer glycol ester monomer, to the product after the copolymerization Further azide, and a click chemical reaction between p-propargyl benzaldehyde obtained by reacting with commercial p-hydroxybenzaldehyde and propargyl bromide, in the presence of aminated modified ferric oxide nanoparticles , to prepare a self-healing hydrogel based on acylhydrazone bonds.

The present invention proposes the preparation of a magnetic field and temperature dual-response intelligent hydrogel based on the dynamic reversible self-repair of the acylhydrazone bond. The specific steps are as follows:

(1) Add pentaerythritol and triethylamine sequentially to an appropriate amount of anhydrous solvent A at a molar ratio of 1:6, and process the system for 3 to 6 rounds by extracting argon or nitrogen to exclude air to obtain a suspension; Under ice-bath conditions, 2-bromoisobutyryl bromide in an equimolar amount to triethylamine was added dropwise to the above suspension, and magnetically stirred at room temperature for more than 12 hours. After the reaction, extract, recrystallize, wash and dry to obtain the initiator;

(2) Mix diethylene glycol monomethyl ether methacrylate (MEO ₂ MA) and oligoethylene glycol methacrylate (OEGMA) at a ratio of 95:5~85:15, mix monomers and step (1 ), the initiator obtained in ) was dissolved in an appropriate amount of anhydrous solvent B at a molar ratio of 30:1 to 40:1, and a complexing agent pentamethyldiethylenetriamine (pentamethyldiethylenetriamine) ( PMDETA) and catalyst cuprous bromide, the system was treated for 3-6 rounds by extracting argon or nitrogen to exclude air; the system was under magnetic stirring, the reaction temperature was controlled at 60°C, and the reaction time was 4-8 hours. After the reaction, dialyze and freeze-dry;

(3) Dissolve the product obtained in step (2) and sodium azide in an appropriate amount of anhydrous solvent C at a molar ratio of 1:20~1:40, and control the reaction temperature at 45~60°C under magnetic stirring. The reaction time is more than 48 hours. After the reaction, column chromatography purification, precipitation, and vacuum drying;

(4) Dissolve p-hydroxybenzaldehyde and potassium carbonate in an appropriate amount of solvent D at a molar ratio of 1:2, mix well and add propargyl bromide dissolved in solvent E, the mixture of propargyl bromide and p-hydroxybenzaldehyde The molar ratio is 1:1, and the system is reacted at 60°C for 3 hours under magnetic stirring. After the reaction is completed, precipitate, wash, and vacuum dry;

(5) Dissolve the product obtained in step (3) and step (4) in an appropriate amount of solvent F at a molar ratio of 4:1, and add cuprous bromide and Pentamethyldiethylenetriamine, filled with nitrogen or argon and evacuated for 3~6 rounds, reacted at a temperature of 50~70°C for more than 48 hours, after the reaction, dialyzed and precipitated;

(6) Under the protection of nitrogen, dissolve FeCl ₂ 4H ₂ O and FeCl ₃ 6H ₂ O in an appropriate amount of deionized water at a molar ratio of 1:1.7~1:2, add oleic acid, mix well, and heat to Stir vigorously at 80~100°C for more than 30 minutes, quickly add an appropriate amount of ammonia water to the reactant, continue to stir at 80~100°C for 2~3 hours, cool to room temperature after the reaction, centrifuge, wash, and dry; Triferroic nanoparticles;

(7) Ultrasonic disperse ferric oxide nanoparticles obtained in step (6) in an appropriate amount of deionized water, add 2,3-diaminophenol and ammonia water and continue ultrasonic dispersion to obtain a uniformly dispersed suspension; the system is at 80~ Stir mechanically at 100°C for 30-60 minutes. After the reaction is completed, cool to room temperature, apply a magnetic field to collect, wash, and dry;

(8) Ultrasonic disperse the product obtained in step (7) in an appropriate amount of deionized water, then add the product obtained in step (5), fully dissolve, and stir the system magnetically at high temperature, reflux, react for 3-6 hours, and cool to Stand at room temperature for 3-6 hours to obtain the final hydrogel product.

In the present invention, the anhydrous solvent A described in step (1) is tetrahydrofuran.

In the present invention, the anhydrous solvent B in step (2) is one or more of N,N-dimethylformamide, N,N-diethylformamide or N,N-dimethylacetamide kind.

In the present invention, the anhydrous solvent C in step (3) is one or more of N,N-dimethylformamide, N,N-diethylformamide or N,N-dimethylacetamide kind.

In the present invention, the first anhydrous solvent D in step (4) is one of N,N-dimethylformamide, N,N-diethylformamide or N,N-dimethylacetamide species or several. The solvent E in which propargyl bromide is dissolved is toluene.

In the present invention, the solvent used for precipitation in step (4) is ethanol, and the precipitating agent used for precipitation is n-hexane or cyclohexane.

In the present invention, the solvent F in step (5) is one or more of N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, Or water, or a mixed solvent of water and tert-butanol.

In the present invention, the solvent used for washing in step (6) is deionized water and ethanol.

In the present invention, the solvent used for washing in step (7) is deionized water and ethanol.

The beneficial effect of the present invention is that: the present invention utilizes the dynamic reversible acylhydrazone bonds formed between the aldehyde groups on the polymer and the primary amines on the magnetic particles to finally prepare a temperature-responsive hydrogel with self-healing properties. Under normal temperature and neutral conditions, the gel fragments can be attracted and aggregated by a magnetic field, and repaired through the formation of acylhydrazone bonds to restore the gel as a whole. Therefore, it has wide application potential in improving the service life of materials and drug delivery. The preparation method of the invention has high feasibility, easy-to-obtain raw materials, and good development and popularization.

Description of drawings

Fig. 1 is the nuclear magnetic spectrum of embodiment 1 product B.

Fig. 2 is the infrared spectrogram of the product C of Example 1, and there is a weak azide vibration peak at 1987cm ^-1 .

3 is a schematic diagram of the dynamic reversibility of the acylhydrazone bond of the magnetic field and temperature dual-responsive smart hydrogel based on the dynamic reversible self-healing of the acylhydrazone bond prepared in Example 1.

4 is a schematic diagram of the cross-linked structure of the magnetic field and temperature dual-responsive smart hydrogel based on the dynamic reversible self-healing of the acylhydrazone bond prepared in Example 1.

detailed description

The following examples are to further illustrate the present invention, but not to limit the scope of the present invention.

The molecular structure of the magnetic field and temperature dual-response smart hydrogel based on the dynamic reversible self-healing of the acylhydrazone bond was determined by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance analyzer (NMR). The microscopic morphology of the composite hydrogel was determined by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The self-healing efficiency of the composite hydrogel is characterized by the recovery efficiency of mechanical properties.

Example 1

1.36g of pentaerythritol and 8.22mL of triethylamine were dissolved in 50mL of anhydrous tetrahydrofuran, and the system was evacuated at 0°C for 5 rounds. Then, 7.42 mL of 2-bromoisobutyryl bromide dissolved in 10 mL of N,N-dimethylformamide was added dropwise to the above suspension in an ice bath at 0°C, and the addition was completed in about 30 minutes. Stir magnetically for 12 hours at room temperature. Extract with ether, saturated sodium bicarbonate and deionized water to obtain the upper organic solution, dry with magnesium sulfate for 12 hours, filter to obtain a pure solution, and after rotary evaporation, the product is dissolved in petroleum ether for recrystallization, and filtered to obtain a solid product on the filter cake. Washed several times with ethanol, and dried in a vacuum oven at 40°C for 24 hours to obtain product A. Dissolve 18.91g of MEO ₂ MA monomer, 4.15g of OEGMA monomer, 0.5g of product A, 845μL of complexing agent pentamethyldiethylenetriamine in 20mL of anhydrous N,N-dimethylformamide solvent, and then add 0.45g The catalyst is cuprous bromide, and the system is treated for 5 rounds by extracting argon or nitrogen to exclude air. Under magnetic stirring, react at 60° C. for 4 hours. After the reaction, dialyze with a 3500kd dialysis bag for 3 days. After the solution gradually changes from blue to colorless, take it out and freeze-dry for 3 days to obtain product B. Under heating conditions, 19 g of product B was dissolved in 60 mL of anhydrous N,N-dimethylformamide solvent, 6 g of NaN ₃ was added, and magnetically stirred at 45° C. for 48 hours. After the reaction, most of the solvent was evaporated by rotary evaporation, dissolved in a large amount of tetrahydrofuran, and purified by neutral alumina column chromatography. Most of the tetrahydrofuran solvent was evaporated by rotary evaporation, then precipitated with n-hexane, and dried in vacuum at 40° C. for 3 days to obtain product C. Take 1.6g p-hydroxybenzaldehyde, 3.2g potassium carbonate dissolved in 20mL DMF, add 20g propargyl bromide dissolved in toluene, and react the system at 70°C for 2 hours. The product was washed with water and ethanol solution, and dried in a vacuum oven at 40°C for two days to obtain product D. Dissolve 2.0g FeCl ₂ 4H ₂ O and 4.8g FeCl ₃ 6H ₂ O in 30mL deionized water, add 0.85mL oleic acid, stir mechanically at 90°C for 30 minutes, then quickly add 20mL ammonia water with a mass fraction of 14wt% to Among the reactants, the reaction was continued at 90° C. for 2.5 hours. After the reaction was completed, it was cooled to room temperature, washed with ethanol and water, centrifuged three times, and dried in a vacuum oven at 60°C for 2 days to obtain product E. Take 0.1 g of product E and ultrasonically disperse it in 40 mL of deionized water, add 0.3 g of 2,3-diaminophenol and 0.24 mL of ammonia water with a mass fraction of 30 wt%, and continue to ultrasonically disperse to obtain a uniformly dispersed suspension. The system was mechanically stirred at 90°C for 60 minutes. After the reaction, cool to room temperature, apply an external magnetic field to collect the product, and wash with a large amount of water and ethanol to obtain product F. Ultrasonic dispersion of 0.5gF in 60mL of deionized water, 10gD of the product was added and fully dissolved, the system was magnetically stirred at high temperature, refluxed, reacted for 5 hours, cooled to room temperature, and stood for 3 hours to obtain the final hydrogel product.

Example 2

1.36g of pentaerythritol and 8.22mL of triethylamine were dissolved in 70mL of anhydrous tetrahydrofuran, and the system was evacuated at 0°C for 5 rounds. Then, 7.42 mL of 2-bromoisobutyryl bromide dissolved in 20 mL of N,N-dimethylformamide was added dropwise to the above suspension in an ice bath at 0°C, and the addition was completed in about 30 minutes. Stir magnetically for 18 hours at room temperature. Extract with ether, saturated sodium bicarbonate and deionized water to obtain the upper organic solution, dry with magnesium sulfate for 18 hours, filter to obtain a pure solution, and after rotary evaporation, the product is dissolved in petroleum ether for recrystallization, and filtered to obtain a solid product on the filter cake. Washed several times with ethanol, and dried in a vacuum oven at 50°C for 24 hours to obtain product A. Dissolve 37.8g of MEO ₂ MA monomer, 8.3g of OEGMA monomer, 1.0g of product A, 1.7mL of complexing agent pentamethyldiethylenetriamine in 40mL of anhydrous N,N-dimethylformamide solvent, and then add 0.9 g Catalyst cuprous bromide, the system was treated for 5 rounds by extracting argon or nitrogen to exclude air. Under magnetic stirring, react at 50° C. for 8 hours. After the reaction, dialyze with a 3500kd dialysis bag for 3 days. After the solution gradually changes from blue to colorless, take it out and freeze-dry for 3 days to obtain product B. Under heating conditions, 30 g of product B was dissolved in 80 mL of anhydrous N,N-dimethylformamide solvent, 9 g of NaN ₃ was added, and magnetically stirred at 60° C. for 60 hours. After the reaction, most of the solvent was evaporated by rotary evaporation, dissolved in a large amount of tetrahydrofuran, and purified by neutral alumina column chromatography. Most of the tetrahydrofuran solvent was evaporated by rotary evaporation, then precipitated with n-hexane, and dried in vacuum at 40° C. for 3 days to obtain product C. Take 0.8g of p-hydroxybenzaldehyde, 1.6g of potassium carbonate dissolved in 10mL of DMF, add 1g of propargyl bromide dissolved in toluene, and react the system at 70°C for 2.5 hours. The product was washed with water and ethanol solution, and dried in a vacuum oven at 50°C for two days to obtain product D. Dissolve 3.0g FeCl ₂ 4H ₂ O and 7.2g FeCl ₃ 6H ₂ O in 40mL of deionized water, add 1.2mL of oleic acid, and stir mechanically at 90°C for 30 minutes, then quickly add 30mL of ammonia water with a mass fraction of 14wt% to Among the reactants, the reaction was continued at 100° C. for 3 hours. After the reaction was completed, it was cooled to room temperature, washed with ethanol and water, centrifuged three times, and dried in a vacuum oven at 60°C for 2 days to obtain product E. Take 0.5g of product E and ultrasonically disperse it in 40mL of deionized water, add 1.5g of 2,3-diaminophenol and 1.3mL of ammonia water with a mass fraction of 30wt%, and continue to ultrasonically disperse to obtain a uniformly dispersed suspension. The system was mechanically stirred at 100°C for 45 minutes. After the reaction, cool to room temperature, apply an external magnetic field to collect the product, and wash with a large amount of water and ethanol to obtain product F. Ultrasonic dispersion of 1gF in 60mL of deionized water, adding 20g of product D and fully dissolving, the system was magnetically stirred at high temperature, refluxed, reacted for 6 hours, cooled to room temperature, and stood for 4 hours to obtain the final hydrogel product.

Example 3

0.7 g of pentaerythritol and 4.3 mL of triethylamine were dissolved in 40 mL of anhydrous tetrahydrofuran, and the system was evacuated at 0°C for 5 rounds. Then, 3.8 mL of 2-bromoisobutyryl bromide dissolved in 10 mL of N,N-dimethylformamide was added dropwise to the above suspension in an ice bath at 0°C, and the addition was completed in about 20 minutes. Stir magnetically for 12 hours at room temperature. Extract with ether, saturated sodium bicarbonate and deionized water to obtain the upper organic solution, dry with magnesium sulfate for 12 hours, filter to obtain a pure solution, and after rotary evaporation, the product is dissolved in petroleum ether for recrystallization, and filtered to obtain a solid product on the filter cake. Washed several times with ethanol, dried in a vacuum oven at 40°C for 24 hours to obtain product A. Dissolve 9.0g of MEO ₂ MA monomer, 2.2g of OEGMA monomer, 0.25g of product A, 425μL of complexing agent pentamethyldiethylenetriamine in 15mL of anhydrous N,N-dimethylformamide solvent, and then add 0.25g The catalyst is cuprous bromide, and the system is treated for 6 rounds by extracting argon or nitrogen to exclude air. Under magnetic stirring, react at 50° C. for 6 hours. After the reaction, dialyze with a 3500kd dialysis bag for 3 days. After the solution gradually changes from blue to colorless, take it out and freeze-dry for 3 days to obtain product B. Under heating conditions, 10 g of product B was dissolved in 60 mL of anhydrous N,N-dimethylformamide solvent, 3 g of NaN ₃ was added, and magnetically stirred at 60° C. for 36 hours. After the reaction, most of the solvent was evaporated by rotary evaporation, dissolved in a large amount of tetrahydrofuran, and purified by neutral alumina column chromatography. Most of the tetrahydrofuran solvent was evaporated by rotary evaporation, then precipitated with n-hexane, and dried in vacuum at 40° C. for 3 days to obtain product C. Take 0.8g p-hydroxybenzaldehyde, 1.6g potassium carbonate dissolved in 10mL DMF, add 1g propargyl bromide dissolved in toluene, and react the system at 50°C for 4 hours. The product was washed with water and ethanol solution, and dried in a vacuum oven at 40°C for two days to obtain product D. Dissolve 2.0g FeCl ₂ 4H ₂ O and 4.8g FeCl ₃ 6H ₂ O in 30mL of deionized water, add 0.85mL of oleic acid, and stir mechanically at 80°C for 30 minutes, then quickly add 20mL of ammonia water with a mass fraction of 14wt% to Among the reactants, the reaction was continued at 80° C. for 3 hours. After the reaction was completed, it was cooled to room temperature, washed with ethanol and water, centrifuged three times, and dried in a vacuum oven at 50°C for 2 days to obtain product E. Take 1 g of product E and ultrasonically disperse it in 40 mL of deionized water, add 3 g of 2,3-diaminophenol and 2.4 mL of ammonia water with a mass fraction of 30 wt%, and continue ultrasonic dispersion to obtain a uniformly dispersed suspension. The system was mechanically stirred at 90°C for 60 minutes. After the reaction, cool to room temperature, apply an external magnetic field to collect the product, and wash with a large amount of water and ethanol to obtain product F. Ultrasonic dispersion of 3gF in 80mL deionized water, adding 25gD of the product and fully dissolving, the system was magnetically stirred at high temperature, refluxed, reacted for 6 hours, cooled to room temperature, and stood for 4 hours to obtain the final hydrogel product.

Claims (9)

1. A method for preparing a magnetic field and temperature dual-response intelligent hydrogel based on the dynamic reversible self-repairing of the acylhydrazone bond, characterized in that the specific steps are as follows: (1) Add pentaerythritol and triethylamine sequentially to an appropriate amount of anhydrous solvent A at a molar ratio of 1:6, and process the system for 3 to 6 rounds by extracting argon or nitrogen to exclude air to obtain a suspension; Under ice-bath conditions, add 2-bromoisobutyryl bromide in an equimolar amount to triethylamine dropwise to the above suspension, and stir magnetically for more than 12 hours at room temperature. After the reaction, extract, recrystallize, wash and dry, get the initiator; (2) Mix MEO ₂ MA and OEGMA at a ratio of 95:5~85:15, and dissolve the mixed monomer and the initiator obtained in (1) in an appropriate amount of anhydrous solvent B at a molar ratio of 30:1~40:1 , adding a complexing agent pentamethyldiethylenetriamine (PMDETA) and a catalyst cuprous bromide in a slightly excess molar amount compared to the initiator in step (1), and the system is treated for 3 to 6 rounds by extracting argon or nitrogen to exclude air; The system is under magnetic stirring, the reaction temperature is controlled at 60°C, and the reaction time is 4-8 hours. After the reaction is completed, dialyze and freeze-dry; (3) Dissolve the product obtained in step (2) and sodium azide in an appropriate amount of anhydrous solvent C at a molar ratio of 1:20~1:40, and control the reaction temperature at 45~60°C under magnetic stirring. The reaction time is more than 48 hours. After the reaction, column chromatography purification, precipitation, and vacuum drying; (4) Dissolve p-hydroxybenzaldehyde and potassium carbonate in an appropriate amount of solvent D at a molar ratio of 1:2, mix well and add propargyl bromide dissolved in solvent E, the mixture of propargyl bromide and p-hydroxybenzaldehyde The molar ratio is 1:1, and the system is reacted at 60°C for 3 hours under magnetic stirring. After the reaction is completed, precipitate, wash, and vacuum dry; (5) Dissolve the product in step (3) and step (4) in an appropriate amount of solvent F at a molar ratio of 4:1, and add cuprous bromide and pentaquinone in a molar ratio equal to that of the product in step (3). Methyldiethylenetriamine, filled with nitrogen or argon for 3~6 rounds of vacuuming, reacted at a temperature of 50~70°C for more than 48 hours, after the reaction, dialyzed and precipitated; (6) Under the protection of nitrogen, dissolve FeCl ₂ 4H ₂ O and FeCl ₃ 6H ₂ O in an appropriate amount of deionized water at a molar ratio of 1:1.7~1:2, add oleic acid, mix well, and heat to Stir vigorously at 80~100°C for more than 30 minutes, quickly add an appropriate amount of ammonia water to the reactant, continue to stir at 80~100°C for 2~3 hours, cool to room temperature after the reaction, centrifuge, wash, and dry to obtain tetraoxide Triferroic nanoparticles; (7) Ultrasonic disperse ferric oxide nanoparticles obtained in step (6) in an appropriate amount of deionized water, add 2,3-diaminophenol and ammonia water and continue ultrasonic dispersion to obtain a uniformly dispersed suspension; the system is at 80~ Stir mechanically at 100°C for 30-60 minutes, cool to room temperature after the reaction, collect with an external magnetic field, wash, and dry; (8) Ultrasonic disperse the product obtained in step (7) in an appropriate amount of deionized water, then add the product obtained in step (5), fully dissolve, and stir the system magnetically at high temperature, reflux, react for 3-6 hours, and cool to room temperature and allowed to stand for 3-6 hours to obtain the final hydrogel product. 2. A method for preparing a magnetic field and temperature dual-response intelligent hydrogel based on acylhydrazone bond dynamic reversible self-healing according to claim 1, characterized in that the anhydrous solvent A is tetrahydrofuran. 3. A kind of preparation method based on acylhydrazone bond dynamic reversible self-healing magnetic field, temperature double response type intelligent hydrogel according to claim 1, it is characterized in that anhydrous solvent B is N,N-dimethyl formazan One or more of amides, N, N-diethylformamide or N, N-dimethylacetamide. 4. A method for preparing a magnetic field and temperature dual-response intelligent hydrogel based on acylhydrazone bond dynamic reversible self-healing according to claim 1, characterized in that the anhydrous solvent C is N,N-dimethyl formazan One or more of amides, N, N-diethylformamide or N, N-dimethylacetamide. 5. The preparation method of a dynamic reversible self-repairing based on acylhydrazone bond according to claim 1, characterized in that the anhydrous solvent D is N,N-dimethyl formazan One or more of amides, N, N-diethylformamide or N, N-dimethylacetamide. 6. The preparation method of a dynamic reversible self-repairing based on acylhydrazone bond according to claim 1, characterized in that the solvent E in which propargyl bromide is dissolved is toluene. 7. A method for preparing a dynamic reversible self-repairing based on acylhydrazone bond according to claim 1, characterized in that the solvent F is N,N-dimethylformamide, One or more of N, N-diethylformamide, N, N-dimethylacetamide, or water, or a mixed solvent of water and tert-butanol. 8. A method for preparing a magnetic field and temperature dual-response smart hydrogel based on dynamic reversible self-healing of acylhydrazone bonds according to claim 1, characterized in that the solvent used for precipitation in step (4) is ethanol, and the solvent used for precipitation is ethanol. Precipitating agent is n-hexane or cyclohexane. 9. A method for preparing a dynamic reversible self-healing magnetic field and temperature dual-response smart hydrogel based on acylhydrazone bonds according to claim 1, characterized in that the solvents used for washing in steps (6) and (7) are both for deionized water and ethanol.