Preparation method of dry-resistant and anti-freezing high-adhesion biomimetic hydrogel

Abstract

The application discloses a preparation method of a dry-proof and anti-freezing high-adhesion biomimetic hydrogel, which is composed of grafted functional polyacrylic acid and doped effective anti-freezing factors; the grafted functional polyacrylic acid is prepared by an amidation reaction of -NH2 of levodopa and -COOH of polyacrylic acid under catalysis of EDC and NHS; and the effective anti-freezing factors are composed of glucose and ionic liquid; the dry-proof and anti-freezing high-adhesion biomimetic hydrogel has good water retention, anti-freezing property, excellent adhesion and reusability, and can be used for bonding various inorganic (ceramic, glass) or organic material objects (plastic, rubber) and the like, is suitable for fields of bondable biomimetic flexible sensors and biomimetic electronic functional skin and the like, and solves the problems of ordinary hydrogels, such as fast water loss, no anti-freezing property and weak adhesion, thereby opening up a new road for the construction and application of various flexible sensor devices.

Description

Technical Field

[0001] This invention belongs to the field of intelligent flexible material preparation technology, and particularly relates to a method for preparing a dry-resistant, freeze-resistant, highly adhesive biomimetic hydrogel. Background Technology

[0002] Since the concept of "electronic wearable devices" was proposed in the 1970s, they have shown broad application prospects in fields such as human body monitoring due to their advantages such as flexibility, accuracy, and instant alerts. Typically, electronic wearable devices consist of sensing materials, conversion elements, and signal analysis circuits, with the sensing material being the core structure. Currently, rigid materials are widely used in sensing elements due to their high reliability and strong load-bearing capacity, but they suffer from problems such as mismatch in mechanical strength at the device / skin interface, discomfort during wear, and insufficient biocompatibility. Compared to traditional rigid sensors, flexible materials have advantages such as small size, light weight, good flexibility, and high sensitivity. They can be directly attached to the surface of human skin and achieve in-situ monitoring of human physiological information. Therefore, they have a very large development and application prospect in the future field of "electronic wearable devices."

[0003] Hydrogels are materials with a three-dimensional network structure composed of water and polymer segments. They not only have good elasticity and stretchability, but also ion conduction properties. The elasticity and stretchability can be well integrated with biological organisms; the excellent ion conduction characteristics can convert the collected sensing signals into analyzable electrical signals; in addition, hydrogels have excellent biocompatibility, so they have great advantages in constructing flexible sensors and are an ideal choice for developing next-generation flexible wearable devices. However, ordinary hydrogels suffer from problems such as rapid water loss, lack of freeze protection, and weak adhesion. Therefore, inspired by mussel biomaterials, this invention introduces the effective component, catechol groups, into the polyacrylic acid molecular chain to prepare a desiccation-resistant, freeze-resistant, and highly adhesive biomimetic hydrogel. It has good water retention, freeze resistance, excellent adhesion, and reusability, including bonding various inorganic (ceramic, glass) or organic materials (pigskin: mimicking human skin), etc. It is suitable for bonding biomimetic flexible sensors and biomimetic electronic functional skin, solving the problems of rapid water loss, lack of freeze protection, and weak adhesion of ordinary hydrogels, and opening up new avenues for the construction and application of various flexible sensor devices. Summary of the Invention

[0004] Technical problems to be solved:

[0005] To address the shortcomings of existing technologies, this application provides a method for preparing a desiccation-resistant, freeze-resistant, highly adhesive biomimetic hydrogel, which solves the problems of rapid water loss, lack of freeze protection, and weak adhesion.

[0006] Technical solution:

[0007] To achieve the above objectives, this application provides the following technical solution:

[0008] A method for preparing a desiccation-resistant, freeze-resistant, highly adhesive biomimetic hydrogel, wherein the raw material of the desiccation-resistant, freeze-resistant, highly adhesive biomimetic hydrogel includes grafted functionalized polyacrylic acid and an antifreeze agent, comprising the following steps:

[0009] Step A: Prepare grafted functionalized polyacrylic acid;

[0010] Step B: Weigh acrylamide, grafted functionalized polyacrylic acid, antifreeze agent, deionized water, N,N-methylenebisacrylamide and photoinitiator into a glass bottle and stir well.

[0011] Step C, then purge with nitrogen for 5 minutes, and finally cure with LED ultraviolet light for 30 minutes to obtain a dry-resistant, freeze-resistant, highly adhesive biomimetic hydrogel.

[0012] Preferably, the grafted functionalized polyacrylic acid has the following general formula:

[0013]

[0014] Preferably, the grafted functionalized polyacrylic acid is prepared from raw materials prepared by the following steps and in the following mass ratios:

[0015] Step a: Weigh out polyacrylic acid, EDC, NHS, and dimethyl sulfoxide (DMSO) and add them sequentially to a glass bottle. Mix thoroughly, maintain the temperature at 35°C, and stir until dissolved. The mass ratio of polyacrylic acid to EDC is 1:2 to 2.8.

[0016] The mass ratio of DMSO to NHS is 1:1, and the amount of DMSO used is 400% to 600% of the total mass of polyacrylic acid, EDC and NHS.

[0017] Step b: Weigh out L-DOPA and solvent and add them to a glass bottle in sequence. Mix them evenly and control the temperature at 35°C while stirring to dissolve. The amount of L-DOPA used is 25% of the mass of polyacrylic acid. The mass ratio of L-DOPA to solvent is 1:35. The solvent is composed of DMSO and water, and the ratio of DMSO to water is 2 to 3:5.

[0018] Step c: Slowly add the solution dissolved in step b to the solution prepared in step a at a rate of 2 mL / min, and then stir the reaction in a 30°C water bath for 48 h.

[0019] Step d: First, boil the dialysis bag in deionized water for 10 minutes, then remove it and soak it in deionized water for 30 minutes. Then, pour the solution from step c (after stirring and reacting) into the dialysis bag and dialyze it in deionized water for 2 days, changing the deionized water every 12 hours. Finally, remove excess water from the dialyzed solution using a rotary evaporator to obtain a concentrated liquid. Then, dry it in an oven to obtain grafted functionalized polyacrylic acid. Specifically, the grafted functionalized polyacrylic acid is L-DOPA grafted functionalized polyacrylic acid. The dialysis bag is a 500 molecular weight cutoff type, and the oven temperature is 65℃.

[0020] Preferably, the antifreeze factor is composed of glucose and an ionic liquid, wherein the ionic liquid is 1-butyl-3-methylimidazolium chloride ([BMIm]Cl), and the mass ratio of glucose to [BMIm]Cl is 2 to 3.5:1.

[0021] Preferably, the anti-drying, anti-freezing, highly adhesive biomimetic hydrogel is prepared from the following raw materials in parts by weight:

[0022] The mass ratio of acrylamide, grafted functionalized polyacrylic acid, and antifreeze factor is 4:2 to 3:4. The amount of N,N-methylenebisacrylamide is 0.1% of the mass of acrylamide, the amount of deionized water is 200% to 250% of the total mass of acrylamide, grafted functionalized polyacrylic acid, and antifreeze factor, and the amount of photoinitiator is 1% of the total mass of acrylamide, grafted functionalized polyacrylic acid, and antifreeze factor.

[0023] Preferably, the photoinitiator is one or more of 4-acryloyloxybenzophenone, ethyl 4-dimethylaminobenzoate, and 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0024] Preferably, the photocuring of the LED ultraviolet lamp is performed at a wavelength of 365–390 nm, and the radiation dose of the LED ultraviolet lamp is 350–500 mW / cm². 2 .

[0025] Preferably, step B specifically involves weighing 0.4g acrylamide, 0.2g grafted functionalized polyacrylic acid, 0.4g antifreeze factor, 2g deionized water, 0.0004g N,N-methylenebisacrylamide, and 0.01g 4-acryloyloxybenzophenone into a glass bottle and stirring until homogeneous; the antifreeze factor is composed of 0.267g glucose and 0.133g [BMIm]Cl.

[0026] Preferably, step C specifically involves purging with nitrogen for 5 minutes, followed by curing with an LED ultraviolet lamp at 365nm for 30 minutes, with a UV radiation dose of 350mW / cm². 2 Ultimately, a highly adhesive biomimetic hydrogel with anti-drying and anti-freezing properties was obtained.

[0027] The principle of this invention is as follows: grafted functionalized polyacrylic acid is prepared by an amidation reaction between the -NH2 group of levodopa and the -COOH group of polyacrylic acid under the catalysis of EDC and NHS. The reaction mechanism is as follows: EDC first reacts with the carboxyl group to generate an active intermediate, the intermediate then reacts with NHS to generate an NHS ester intermediate, and then the carboxyl and amino groups undergo a dehydration reaction to generate amide bonds, and finally the amidation reaction occurs.

[0028] Beneficial effects:

[0029] This application provides a method for preparing a desiccation-resistant, freeze-resistant, highly adhesive biomimetic hydrogel, which has the following beneficial effects:

[0030] 1. The present invention provides a high-adhesion biomimetic hydrogel with good water retention, antifreeze properties, excellent adhesion and reusability, including: bonding various inorganic (ceramic, glass) or organic material objects (pigskin: imitation human skin), etc.

[0031] 2. It is suitable for applications such as adhesive bionic flexible sensors and bionic electronic functional skin, solving problems such as rapid water loss, lack of antifreeze properties, and weak adhesion of ordinary hydrogels.

[0032] 3. It has opened up new avenues for the construction and application of various flexible sensor devices. Attached Figure Description

[0033] Figure 1 This is the infrared spectrum of the grafted functionalized polyacrylic acid of this application.

[0034] Figure 2 This is a real image of a biomimetic hydrogel that is anti-drying, anti-freezing, and highly adhesive. The left image is of the hydrogel before UV curing, and the right image is of the hydrogel after UV curing.

[0035] Figure 3 The images show the anti-drying effect of a high-adhesion biomimetic hydrogel with anti-drying and anti-freezing properties. The left image shows the anti-drying effect of a common hydrogel, while the right image shows the anti-drying effect of the biomimetic hydrogel with anti-drying and anti-freezing properties of the present invention.

[0036] Figure 4 The images show the antifreeze effect of a high-adhesion biomimetic hydrogel that is resistant to dryness and freezing. The left image shows the antifreeze effect of a regular hydrogel at -25℃, while the right image shows the antifreeze effect of the resistant-to-dryness and freezing-resistant biomimetic hydrogel of this invention at -25℃.

[0037] Figure 5This image shows a schematic diagram of a dry-resistant, freeze-resistant, highly adhesive biomimetic hydrogel and its bonding strength data. The left image shows a schematic diagram of the dry-resistant, freeze-resistant, highly adhesive biomimetic hydrogel bonded to a glass substrate, the lower left image shows a schematic diagram of the hydrogel bonding to a PTFE substrate, the upper right image shows a schematic diagram of the hydrogel bonding to a PP substrate, and the lower right image shows a schematic diagram of the hydrogel bonding to a rubber substrate. The right image shows the bonding strength data of the dry-resistant, freeze-resistant, highly adhesive biomimetic hydrogel. Detailed Implementation

[0038] The preferred embodiments of the present invention are described below. It should be understood that the preferred embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0039] All raw materials used in this invention are commercially available.

[0040] Example 1:

[0041] A method for preparing a desiccation-resistant, freeze-resistant, highly adhesive biomimetic hydrogel includes the following steps:

[0042] Step A, Preparation of grafted functionalized polyacrylic acid:

[0043] Step a: Weigh 2g of polyacrylic acid, 4g of EDC, 4g of NHS and 40g of dimethyl sulfoxide (DMSO) and add them to a glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0044] Step b: Weigh 0.5g of levodopa, 5g of DMSO and 12.5g of water and add them to the glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0045] Step c: Slowly add the solution prepared in step b to the solution in step a, at a dropping rate of 2 mL / min.

[0046] Then, maintain the reaction in a 30°C water bath environment with stirring for 48 hours;

[0047] Step d: First, boil the dialysis bag with a molecular weight cutoff of 500 in deionized water for 10 minutes, then take it out and soak it in deionized water for 30 minutes. Then, pour the solution after the reaction in step c into the dialysis bag and dialyze it in a large amount of deionized water for 2 days, changing the deionized water every 12 hours. Finally, use a rotary evaporator to remove excess water from the dialyzed solution to obtain a concentrated liquid. Then, dry it in a 60°C oven to obtain L-DOPA-grafted functionalized polyacrylic acid.

[0048] Step B: Weigh 0.4g acrylamide, 0.2g grafted functionalized polyacrylic acid, 0.4g antifreeze factor (0.267g glucose, 0.133g [BMIm]Cl), 2g deionized water, 0.0004g N,N-methylenebisacrylamide and 0.01g 4-acryloyloxybenzophenone into a glass bottle and stir well;

[0049] Step C, then purge with nitrogen for 5 minutes, and finally cure with an LED UV lamp at 365nm for 30 minutes, with a UV radiation dose of 350mW / cm². 2 The final product was a biomimetic hydrogel that is resistant to drying and freezing and has high adhesion.

[0050] Example 2:

[0051] A method for preparing a desiccation-resistant, freeze-resistant, highly adhesive biomimetic hydrogel includes the following steps:

[0052] Step A, Preparation of grafted functionalized polyacrylic acid:

[0053] Step a: Weigh 2g of polyacrylic acid, 5g of EDC, 5g of NHS and 60g of dimethyl sulfoxide (DMSO) and add them to a glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0054] Step b: Weigh 0.5g of levodopa, 6.5652g of DMSO and 10.9375g of water and add them to the glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0055] Step c: Slowly add the solution dissolved in step b to the solution in step a at a rate of 2 mL / min, and then stir the reaction in a 30°C water bath for 48 h.

[0056] Step d: First, boil the dialysis bag (molecular weight cutoff type 500) in boiling deionized water for 10 minutes, then take it out and soak it in deionized water for 30 minutes. Then, pour the solution after the reaction in step c into the dialysis bag and dialyze it in a large amount of deionized water for 2 days, changing the deionized water every 12 hours. Finally, use a rotary evaporator to remove excess water from the dialyzed solution to obtain a concentrated liquid. Then, dry it in a 60°C oven to obtain L-DOPA grafted functionalized polyacrylic acid.

[0057] Step B: Weigh 0.4g acrylamide, 0.25g grafted functionalized polyacrylic acid, 0.4g antifreeze factor (0.4g glucose, 0.1g [BMIm]Cl), 2.625g deionized water, 0.0004g N,N-methylenebisacrylamide and 0.0105g ethyl 4-dimethylaminobenzoate into a glass bottle and stir well;

[0058] Step C, then purge with nitrogen for 5 minutes, and finally cure with an LED UV lamp at 380nm for 30 minutes, with a UV radiation dose of 400mW / cm². 2 The final product was a biomimetic hydrogel that is resistant to drying and freezing and has high adhesion.

[0059] Example 3:

[0060] A method for preparing a desiccation-resistant, freeze-resistant, highly adhesive biomimetic hydrogel includes the following steps:

[0061] Step A, Preparation of grafted functionalized polyacrylic acid:

[0062] Step a: Weigh 2g of polyacrylic acid, 5.6g of EDC, 5.6g of NHS and 79.2g of dimethyl sulfoxide (DMSO) and add them to a glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0063] Step b: Weigh 0.5g of levodopa, 6.5652g of DMSO and 10.9375g of water and add them to the glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0064] Step c: Slowly add the solution dissolved in step b to the solution in step a at a rate of 2 mL / min, and then stir the reaction in a 30°C water bath for 48 h.

[0065] Step d: First, boil the dialysis bag (molecular weight cutoff type 500) in boiling deionized water for 10 minutes, then take it out and soak it in deionized water for 30 minutes. Then, pour the solution after the reaction in step c into the dialysis bag and dialyze it in a large amount of deionized water for 2 days, changing the deionized water every 12 hours. Finally, use a rotary evaporator to remove excess water from the dialyzed solution to obtain a concentrated liquid. Then, dry it in a 60°C oven to obtain L-DOPA grafted functionalized polyacrylic acid.

[0066] Step B: Weigh 0.4g acrylamide, 0.3g grafted functionalized polyacrylic acid, 0.4g antifreeze factor (0.311g glucose, 0.089g [BMIm]Cl), 2.75g deionized water, 0.0004g N,N-methylenebisacrylamide and 0.011g 2-hydroxy-2-methyl-1-phenyl-1-propanone into a glass bottle and stir well;

[0067] Step C, then purge with nitrogen for 5 minutes, and finally cure with an LED UV lamp at 390nm for 30 minutes, with a UV radiation dose of 450mW / cm². 2 The final product was a biomimetic hydrogel that is resistant to drying and freezing and has high adhesion.

[0068] Example 4:

[0069] A method for preparing a desiccation-resistant, freeze-resistant, highly adhesive biomimetic hydrogel includes the following steps:

[0070] Step A, Preparation of grafted functionalized polyacrylic acid:

[0071] Step a: Weigh 2g of polyacrylic acid, 4g of EDC, 4g of NHS and 40g of dimethyl sulfoxide (DMSO) and add them to a glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0072] Step b: Weigh 0.5g of levodopa, 5g of DMSO and 12.5g of water and add them to the glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0073] Step c: Slowly add the solution dissolved in step b to the solution in step a at a rate of 2 mL / min, and then stir the reaction in a 30°C water bath for 48 h.

[0074] Step d: First, boil the dialysis bag (molecular weight cutoff type 500) in boiling deionized water for 10 minutes, then take it out and soak it in deionized water for 30 minutes. Then, pour the solution after the reaction in step c into the dialysis bag and dialyze it in a large amount of deionized water for 2 days, changing the deionized water every 12 hours. Finally, use a rotary evaporator to remove excess water from the dialyzed solution to obtain a concentrated liquid. Then, dry it in a 60°C oven to obtain L-DOPA grafted functionalized polyacrylic acid.

[0075] Step B: Weigh 0.4g acrylamide, 0.2g grafted functionalized polyacrylic acid, 0.4g antifreeze factor (0.267g glucose, 0.133g [BMIm]Cl), 2g deionized water, 0.0004g N,N-methylenebisacrylamide, 0.005g 4-acryloyloxybenzophenone, and 0.005g ethyl 4-dimethylaminobenzoate into a glass bottle and stir well.

[0076] Step C, then purge with nitrogen for 5 minutes, and finally cure with an LED UV lamp at 365nm for 30 minutes, with a UV radiation dose of 350mW / cm². 2 The final product was a biomimetic hydrogel that is resistant to drying and freezing and has high adhesion.

[0077] Example 5:

[0078] A method for preparing a desiccation-resistant, freeze-resistant, highly adhesive biomimetic hydrogel includes the following steps:

[0079] Step A, Preparation of grafted functionalized polyacrylic acid:

[0080] Step a: Weigh 2g of polyacrylic acid, 4g of EDC, 4g of NHS and 40g of dimethyl sulfoxide (DMSO) and add them to a glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0081] Step b: Weigh 0.5g of levodopa, 5g of DMSO and 12.5g of water and add them to the glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0082] Step c: Slowly add the solution dissolved in step b to the solution in step a at a rate of 2 mL / min, and then stir the reaction in a 30°C water bath for 48 h.

[0083] Step d: First, boil the dialysis bag (molecular weight cutoff type 500) in boiling deionized water for 10 minutes, then take it out and soak it in deionized water for 30 minutes. Then, pour the solution after the reaction in step c into the dialysis bag and dialyze it in a large amount of deionized water for 2 days, changing the deionized water every 12 hours. Finally, use a rotary evaporator to remove excess water from the dialyzed solution to obtain a concentrated liquid. Then, dry it in a 60°C oven to obtain L-DOPA grafted functionalized polyacrylic acid.

[0084] Step B: Weigh 0.4g acrylamide, 0.2g grafted functionalized polyacrylic acid, 0.4g antifreeze agent (0.267g glucose, 0.133g [BMIm]Cl), 2g deionized water, 0.0004g N,N-methylenebisacrylamide, 0.005g 4-acryloyloxybenzophenone, 0.002g ethyl 4-dimethylaminobenzoate, and 0.003g 2-hydroxy-2-methyl-1-phenyl-1-propanone into a glass bottle and stir until homogeneous;

[0085] Step C, then purge with nitrogen for 5 minutes, and finally cure with an LED UV lamp at 365nm for 30 minutes, with a UV radiation dose of 350mW / cm². 2 The final product was a biomimetic hydrogel that is resistant to drying and freezing and has high adhesion.

[0086] Comparative Example 1

[0087] A non-grafted functionalized polyacrylic acid hydrogel is prepared as follows:

[0088] Weigh 0.4g acrylamide, 0.4g antifreeze (0.267g glucose, 0.133g [BMIm]Cl), 2g deionized water, 0.0004g N,N-methylenebisacrylamide, and 0.01g 4-acryloyloxybenzophenone into a glass bottle and stir well. Then purge with nitrogen for 5 minutes, and finally cure under an LED UV lamp at 365nm for 30 minutes. The UV radiation dose is 350mW / cm². 2The final product was a biomimetic hydrogel that is resistant to drying and freezing and has high adhesion.

[0089] Comparative Example 2

[0090] A method for preparing a hydrogel without antifreeze is described below:

[0091] Step 1: Preparation of grafted functionalized polyacrylic acid

[0092] Step a: Weigh 2g of polyacrylic acid, 4g of EDC, 4g of NHS and 40g of dimethyl sulfoxide (DMSO) and add them to a glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0093] Step b: Weigh 0.5g of levodopa, 5g of DMSO and 12.5g of water and add them to the glass bottle in sequence. Mix well and keep the temperature at 35℃ while stirring to dissolve.

[0094] Step c: Slowly add the solution dissolved in step b to the solution in step a at a rate of 2 mL / min, and then stir the reaction in a 30°C water bath for 48 h.

[0095] Step d: First, boil the dialysis bag (molecular weight cutoff type 500) in boiling deionized water for 10 minutes, then take it out and soak it in deionized water for 30 minutes. Then, pour the solution after the reaction in step c into the dialysis bag and dialyze it in a large amount of deionized water for 2 days, changing the deionized water every 12 hours. Finally, use a rotary evaporator to remove excess water from the dialyzed solution to obtain a concentrated liquid. Then, dry it in a 60°C oven to obtain L-DOPA grafted functionalized polyacrylic acid.

[0096] The second step is to prepare a hydrogel without antifreeze.

[0097] Weigh 0.4g acrylamide, 0.2g grafted functionalized polyacrylic acid, 2g deionized water, 0.0004g N,N-methylenebisacrylamide, and 0.01g 4-acryloyloxybenzophenone into a glass bottle and stir well. Then purge with nitrogen for 5 minutes, and finally cure with an LED ultraviolet lamp at 365nm for 30 minutes. The UV radiation dose is 350mW / cm². 2 The final product was a biomimetic hydrogel that is resistant to drying and freezing and has high adhesion.

[0098] Performance testing:

[0099] Adhesion performance test method: A 3mm thick hydrogel is attached between two transparent glass plates with an overlap area of ​​2cm×2.5cm. Then, a universal testing machine is used to test its shear strength at a tensile rate of 20mm / min.

[0100] The performance characterization of the examples and comparative examples is shown in the table below:

[0101]

[0102] The results from the examples show that a high-adhesion biomimetic hydrogel with good water retention, antifreeze properties, excellent adhesion, and reusability was prepared by grafting functionalized polyacrylic acid and antifreeze agents, which meets the requirements of related fields.

[0103]

[0104] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a dry-resistant and anti-freezing high-adhesion biomimetic hydrogel, characterized in that, The dry and anti-freezing high-adhesion biomimetic hydrogel raw material comprises grafted functionalized polyacrylic acid and an anti-freezing factor, and comprises the following steps: Step A, preparing grafted functionalized polyacrylic acid; Step B, weighing acrylamide, grafted functionalized polyacrylic acid, anti-freezing factor, deionized water, N, N-methylene bisacrylamide and photoinitiator in a glass bottle and stirring uniformly; Step C, then nitrogen is passed for 5 min, and finally cured by an LED ultraviolet light lamp for 30 min, and finally the dry and anti-freezing high-adhesion biomimetic hydrogel is obtained; The grafted functionalized polyacrylic acid has the following general formula: ； The grafted functionalized polyacrylic acid is prepared from the following raw materials and mass fraction ratio: Step a: weigh polyacrylic acid, EDC, NHS and dimethyl sulfoxide DMSO in sequence and mix uniformly in a glass bottle, and dissolve by stirring while controlling the temperature at 35℃; wherein the mass fraction ratio of polyacrylic acid to EDC is 1:2~2.8; the mass fraction ratio of EDC to NHS is 1:1, and the amount of DMSO is 400%~600% of the total mass of polyacrylic acid, EDC and NHS; Step b: weigh levodopa and solvent in sequence and mix uniformly in a glass bottle, and dissolve by stirring while controlling the temperature at 35℃; the amount of levodopa is 25% of the mass of polyacrylic acid, and the mass fraction ratio of levodopa to solvent is 1:35, and the solvent is composed of DMSO and water, wherein the amount ratio of DMSO to water is 2~3:5; Step c: slowly drop the solution dissolved in step b into the solution prepared in step a at a dropping speed of 2 mL / min, and then stir in a 30℃ water bath environment for 48 h; Step d: first boil the dialysis bag in boiling deionized water for 10 min, then take it out and soak in deionized water for 30 min, then pour the solution after stirring in step c into the dialysis bag and dialyze in deionized water for 2 days, and change the deionized water every 12 h, finally remove the excess water from the dialyzed solution by a rotary evaporator, and finally obtain a concentrated liquid, then dry it in an oven, and finally obtain the grafted functionalized polyacrylic acid; the grafted functionalized polyacrylic acid is specifically levodopa grafted functionalized polyacrylic acid; the dialysis bag is a 500 type with a molecular weight cut-off, and the oven temperature is 65℃; The anti-freezing factor is composed of glucose and ionic liquid, and the ionic liquid is 1-butyl-3-methylimidazolium chloride [BMIm]Cl, wherein the mass ratio of glucose to [BMIm]Cl is 2~3.5:

1.

2. The method of claim 1, wherein the method is characterized by: The dry and anti-freezing high-adhesion biomimetic hydrogel is prepared from the following mass fraction of raw materials: the mass fraction ratio of acrylamide, grafted functionalized polyacrylic acid and anti-freezing factor is 4:2~3:4, the amount of N, N-methylene bisacrylamide is 0.1% of the mass of acrylamide, the amount of deionized water is 200%~250% of the total mass of acrylamide, grafted functionalized polyacrylic acid and anti-freezing factor, and the amount of photoinitiator is 1% of the total mass of acrylamide, grafted functionalized polyacrylic acid and anti-freezing factor.

3. The method of claim 2, wherein the method is characterized by: The photoinitiator is one or more of 4-acryloyloxybenzophenone, 4-dimethylamino- benzoic acid ethyl ester, 2-hydroxy-2-methyl-1-phenyl-1-propanone.

4. The method of claim 1, wherein the method is characterized by: The light curing of the LED ultraviolet light lamp is at a wavelength of 365-390 nm, and the irradiance of the LED ultraviolet light lamp is 350-500 mW / cm 2 .

5. The method of claim 1, wherein the method is characterized by: The specific step B is weighing 0.4 g of acrylamide, 0.2 g of grafted functional polyacrylic acid, 0.4 g of antifreeze factor, 2 g of deionized water, 0.0004 g of N, N-methylene bisacrylamide and 0.01 g of 4-acryloyloxybenzophenone in a glass bottle and stirring uniformly; the antifreeze factor is composed of 0.267 g of glucose and 0.133 g of [BMIm]Cl.

6. The method of claim 1, wherein the method is characterized by: The specific step C is then nitrogen for 5 min, finally cured with LED ultraviolet light 365 nm for 30 min, UV irradiance is 350 mW / cm 2 Finally, the anti-drying and anti-freezing high-adhesion biomimetic hydrogel is obtained.

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