CN114957538B - Self-healing gel based on dynamic non-covalent bond effect and preparation method and application thereof - Google Patents
Self-healing gel based on dynamic non-covalent bond effect and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/103—Detecting, measuring or recording devices for testing the shape, pattern, colour, size or movement of the body or parts thereof, for diagnostic purposes
- A61B5/11—Measuring movement of the entire body or parts thereof, e.g. head or hand tremor, mobility of a limb
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
- A61B5/6801—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
- A61B5/6802—Sensor mounted on worn items
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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Abstract
The invention discloses a self-healing gel based on dynamic non-covalent bond effect, and a preparation method and application thereof, and belongs to the technical field of gels. The invention utilizes photoinitiated micelle polymerization technology, in NaCl, dodecyl sodium sulfate solution, octadecyl methacrylate is used as hydrophobic monomer, acrylamide is used as main hydrophilic monomer, acrylic acid is introduced as modified hydrophilic monomer, I2959 is used as photoinitiator, HP (AA-co-AM) series gel simultaneously containing hydrophobic association and hydrogen bond effect is successfully prepared, the introduction of acrylic acid enhances intermolecular hydrogen bond effect in a system network, so that the mechanical property of the gel is obviously improved, the tensile strength is up to 0.46MPa, and meanwhile, the hydrogen bond effect has reversibility, and the self-healing capability of the gel is effectively enhanced. The hydrogel provided by the invention has relatively sensitive tensile strain-resistance change and good repeatability and stability, and the gel prepared by the invention provides a new material for the development of a self-healing flexible strain sensor.
Description
Technical Field
The invention belongs to the technical field of gel, and particularly relates to a self-healing gel based on dynamic non-covalent bond action, and a preparation method and application thereof.
Background
In recent years, research on flexible wearable electronic devices becomes a research hotspot of intelligent materials, and the flexible wearable electronic devices have wide application prospects in aspects of energy storage devices, artificial skin, wearable flexible electronic screens and the like. Flexible, electrically conductive hydrogels are unique materials with three-dimensional network structures that are advantageous as flexible sensor materials due to their excellent biocompatibility and mechanical and electrical properties that more closely approximate biological tissues. It finds wide application in biomedical, human activity monitoring, soft robotics and 3D printing.
In the design work of self-healable hydrogel, the better the mechanical property, the poorer the ability of the gel to heal and recover to the original strength. For example, yan et al (Yan X, chen Q, zhu L, et al journal of MATERIALS CHEMISTRY B.2017; 5 (37): 7683) designed to synthesize gelatin/polyacrylamide hydrogels with high mechanical properties (tensile strength 0.268 MPa), but healed gelatin/polyacrylamide hydrogels can only achieve 53% healing rate. Polyvinyl alcohol/polyacrylamide (PVA/PAM) gels reported by Zhang et al (Zhang Y, song M, diao Y, et al RSC Advances.2016;6 (113): 112468) have a tensile strength of only 0.132MPa, although they achieve 77% healing. For the flexible wearable electronic device of hydrogel, in order to cope with the stress stretching, crack and fracture in the use process, the research and development of the hydrogel with good mechanical property and self-healing property and good strain sensing capability is necessary.
Disclosure of Invention
In view of the above, the present invention aims to provide a self-healing gel based on dynamic non-covalent bond effect, a preparation method and an application thereof, wherein the gel prepared by the present invention has intermolecular reversible hydrophobic association effect and reversible hydrogen bond effect, the dual dynamic non-covalent bond effect maintains good self-healing capability while improving mechanical properties of the gel, strain sensing performance shows good repeatability and stability, and the series of gels prepared by the present invention can be used as a material matrix of a wearable flexible sensor for monitoring human limb movement.
The invention aims at realizing the following steps:
the invention provides a preparation method of self-healing gel based on dynamic non-covalent bond effect, which mainly comprises the following steps:
(1) Adding sodium dodecyl sulfate and NaCl into water according to the mass ratio of 5:1-1:5 to prepare micelle solution, wherein the concentration of NaCl in the micelle solution is 10-100 g/L;
(2) Adding octadecyl methacrylate into the micelle solution prepared in the step (1) to prepare a transparent solution, wherein the concentration of the octadecyl methacrylate in the transparent solution is 0.5-50 g/L;
(3) Adding acrylamide, acrylic acid and a photoinitiator into the transparent solution prepared in the step (2) to prepare a uniform solution, wherein the mass ratio of the octadecyl methacrylate to the acrylamide to the acrylic acid in the uniform solution is 1-10:100:1-15;
(4) And (3) injecting the uniform solution prepared in the step (3) into a mould, and initiating a reaction by ultraviolet light to obtain the self-healing gel with dynamic non-covalent bond effect.
Further, the mass ratio of the sodium dodecyl sulfate to the NaCl in the step (1) is 3:1-1:1.
Further, the concentration of the octadecyl methacrylate in the transparent solution in the step (2) is 1-20 g/L.
Further, the mass ratio of the octadecyl methacrylate to the acrylamide to the acrylic acid in the step (3) is 1-8:100:5-15.
Further, the photoinitiator in the step (3) is I2959, and the addition amount of the I2959 is 0.1-5% of the total mole of the octadecyl methacrylate, the acrylamide and the acrylic acid.
Further, the reaction time in the step (4) is 1 to 10 hours.
Further, the wavelength of the ultraviolet light in the step (4) is 360-370 nm.
In another aspect, the invention provides a self-healing gel prepared by the preparation method.
The invention also provides application of the self-healing gel in preparing a flexible sensor.
Further, the flexible sensor is applied to wearable electronic equipment.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses AM, AA as hydrophilic monomer in polymerizable micelle solution composed of SDS-SMA, ultraviolet light initiated polymerization successfully prepares self-healing HP (AA-co-AM) conductive hydrogel based on dynamic non-covalent bond effect, and researches the performance of the self-healing HP (AA-co-AM) conductive hydrogel. By adjusting the content of the introduced AA, the mechanical property (tensile strength is improved by 48.3%) of the gel is improved under the condition of keeping better self-healing performance, and the gel has good conductivity (the conductivity is 7.3S/m) due to the existence of a certain amount of Na + and Cl - ions in the gel, and the resistance change of the gel has good stability and repeatability when the gel is repeatedly stretched and bent for many times.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described.
FIG. 1 is a schematic diagram of the synthesis of a hydrogel in example 1;
FIG. 2 shows gel FT-IR spectra of different compositions, wherein, (a) HPAA, (b) 30% AA HP (AA-co-AM), (c) 10% AA HP (AA-co-AM), (d) HPAM;
FIG. 3 shows the stress-strain diagram (a) of hydrogels with different AA/AM ratio HP (AA-co-AM) and the effect of AA content on the tensile strength of the gel (b);
FIG. 4 is a graph of HP (AA 10 -co-AM) gel self-healing properties, wherein (a) dumbbell gel, (b) columnar gel;
FIG. 5 is a stress-strain curve of a gel after HP (AA 10 -co-AM) healing, wherein (a) gel healing performance at different temperatures, (b) HPAM is compared to HP (AA 10 -co-AM) healing performance;
FIG. 6 shows the conductivity and sensing properties of HP (AA 10 -co-AM) gels, wherein (a) the conductivities of gels with different NaCl contents, (b) gel conductivity test experiments, (c) gel sensing sensitivity tests, (d) resistance changes of gels under different strains, (e) resistance changes when repeatedly stretched to 300% strain, and (f) 600% strain cycle stretching properties;
FIG. 7 is a diagram of a simulated test of HP (AA 10 -co-AM) gel human body movement, wherein (a) finger flexion and extension, (b) wrist flexion, (c) elbow flexion, and (d) knee flexion and extension are performed.
Detailed Description
The following detailed description of the invention is provided in connection with examples, which are not intended to limit the scope of the invention, but it will be apparent to those skilled in the art that the examples set forth in the following description are merely illustrative of some of the invention and that other similar embodiments are contemplated as falling within the scope of the invention without inventive faculty.
Example 1
2.7G of Sodium Dodecyl Sulfate (SDS) powder and 1.05g of NaCl crystal grains were added to 35mL of deionized water, stirred in a water bath at 35℃for 1 hour to obtain a micelle solution, 0.19g of octadecyl methacrylate (SMA) was further added and stirred in a water bath environment at 35℃for 2 hours to obtain a transparent solution, then Acrylamide (AM) (4 g), acrylic Acid (AA) (0.4 g) and a photoinitiator I2959 (1% mol of total reactant) were dissolved in the above solution, and after sufficient dissolution, transferred into a mold, reacted under 365nm ultraviolet light for 2 hours and taken out to obtain the desired HP (AA 10 -co-AM) gel (the numbers represent the percentage of AA based on the AM mass, the same applies below) with a water content of 80.5%.
In the preparation process, the gel prepared without adding AA monomer is HPAM gel (Hydrophobically Polyacrylamide Hydrogel), and the water content of the series of gels is 79.07% -81.27% when the AA content is 0-20%, so that the change of the water content is small.
Example 2
The hydrogel prepared in example 1 was freeze-dried and ground into powder, and a sample to be measured was prepared by KBr tabletting, and infrared testing was performed at room temperature (the performance test described below was performed at room temperature) using a front Fourier transform infrared spectrometer of Perkinelmer company, USA, with a wave number scan range of 400cm -1—4000cm-1 and a number of scans of 16 times.
The infrared test results of the prepared HP (AA-co-AM) gels with different acrylic acid contents are shown in FIG. 2, curve a represents an HPAA gel (Hydrophobically Polyacrylic acid) without AM, curve b represents an HP (AA 30 -co-AM) gel with an AA mass fraction of 30%, curve c represents an HP (AA 10 -co-AM) gel with an AA mass fraction of 10%, and curve d represents an HPAM gel without AA. The peak at 3435 cm -1、3205cm-1、3427cm-1、3203cm-1 in the figure belongs to the association peak of amine groups (N-H) in the Acrylamide Molecule (AM) structure and hydroxyl groups (O-H) in the system; peaks at 2919cm -1、2850cm-1 correspond to C-H asymmetric stretching vibration and symmetric stretching vibration of methyl and methylene; the peak at 1662cm -1 corresponds to the C=O telescopic absorption peak of the amide group, and 1454cm -1 is the in-plane bending vibration absorption peak of C-N, which shows that the polymer contains a polyacrylamide chain segment structure, namely AM participates in polymerization reaction; 1714cm -1 is the peak of C=O in acrylic acid, and the content of acrylic acid in the gel represented by b and C is reduced, the intensity of the peak is also reduced, which indicates that AA also participates in polymerization reaction; and 1221cm -1 belongs to the telescopic vibration peak of sulfate radical (OSO 3 -) in the Sodium Dodecyl Sulfate (SDS) remaining in the polymer gel system. The infrared results indicate that the AA segment was successfully incorporated into the HPAM gel.
Example 3
The hydrogel prepared in example 1 was cut into dumbbell-shaped bars (35 mm. Times.2 mm) using a cutter, uniaxially stretched using a WDW-20 universal stretching tester from Oriental laboratory instruments, jinan, at a speed of 100mm/min until the hydrogel broke from the middle, the tensile strength R m and elongation at break were recorded, and 5 samples were selected for each group for parallel testing.
The effect of acrylic acid content on the mechanical properties of HP (AA-co-AM) hydrogels is shown in FIG. 3, and the tensile strength of the hydrogels is increased from 0.31MPa to 0.46MPa in the process that the acrylic acid addition amount in the system is increased from 0 to 10% of the AM mass. The method is characterized in that due to the introduction of the acrylic acid, on one hand, the concentration of the monomers participating in the reaction is increased, the molecular weight is increased, and the molecular chain crosslinking is tighter, so that the tensile strength and the elongation at break of the hydrogel are improved. On the other hand, the introduction of the acrylic acid leads carboxyl functional groups (-COOH) to be introduced into gel copolymer molecular chains, the carboxyl groups form hydrogen bonding action with each other or carboxyl groups form hydrogen bonding action with amide groups (-NH 2), and the hydrogen bonding between the molecular chain segments leads stable network structures (figure 1) to be formed in the gel, so that the tensile strength and the elongation at break of the hydrogel are improved within a certain range. While as AA increases from 10% to 20% of AM mass, hydrogen bonding becomes excessive, gel stiffness increases, and tensile strength and elongation at break of the hydrogel are reduced. Therefore, the tensile strength of HPAM gel can be effectively improved by introducing a certain amount of AA chain segments. The water content of the gel has a great influence on the mechanical properties, the water content obtained by calculating the HP (AA 10 -co-AM) gel is about 80.53%, the change of the water content of the gel along with the change of the AA is very small (79.07% -81.27%), and the influence on the mechanical properties of the gel is weak.
Example 4
The hydrogel prepared in example 1 was cut into two halves, and then the sections were fully bonded together, placed in a mold, healed for 24 hours under different temperature conditions, then removed, cut into dumbbell-shaped bars, and tested in parallel with 5 samples per group. The healing rate of the hydrogel was calculated using equation (1).
Wherein R mh represents the tensile strength of the healing gel and R m0 represents the tensile strength of the original gel.
As a result, as shown in FIG. 4a, HP (AA 10 -co-AM) gel was cut into dumbbell shape (35 mm. Times.2 mm) and dyed with methyl blue and rhodamine B, respectively, and after cutting the gel of different colors, the sections of different colors were allowed to come into contact again and hold for 24 hours, and the healed gel could be stretched to 10 times of the original length without breaking, showing a better healing ability. And, as shown in fig. 4b, the prepared cylindrical hydrogel (diameter 10 mm) can also bear the weight of 200g weight without breaking after healing, which indicates that the prepared HP (AA 10 -co-AM) hydrogel has good self-healing performance.
The healing performance of the gel at different temperatures is shown in fig. 5b and table 1, the healing capacity of the gel after the AA chain segment is introduced is higher than that of the HPAM gel, and under certain environment, when the cut HPAM hydrogel based on hydrophobic association is contacted with the cross section, the cut micelles are re-associated together due to the hydrophobic association, and free non-association blocks in the system are re-aggregated at the cross section, so that the gel can be healed. Meanwhile, after acrylic acid with carboxyl (-COOH) is introduced into an HPAM gel system, reversible hydrogen bonding is formed in the gel by the carboxylic acid groups, and the hydrogen bonding between the macromolecular chain segments at the section can be re-linked in the healing process of the gel. In the absence of AA, gel self-healing is mainly based on hydrophobic association, and introducing AA increases intermolecular hydrogen bonding between carboxyl and amino on acrylamide groups, thereby jointly improving healing performance. Therefore, compared with HPAM gel without AA, the HP (AA 10 -co-AM) gel has 48.3 percent of mechanical property improvement and good self-healing capacity.
As shown in FIG. 5a and Table 1, the rate of healing of HP (AA 10 -co-AM) gel was 26.1% at room temperature, and increased to 60.9% as the temperature of the healing environment was gradually increased to 60 ℃. On one hand, the rising of the healing temperature enhances the fluidity of a polymer chain segment at a fracture, is beneficial to enhancing the hydrophobic association between the PSMA and the micelle formed by SDS after fracture, and promotes the fracture healing. On the other hand, the reversible hydrogen bonding effect exists between HP (AA 10 -co-AM) chain segments formed by introducing AA, and the hydrogen bonding effect between HP (AA 10 -co-AM) molecular chain segments is stronger along with the increase of temperature, so that the effect between functional groups in a polymer chain is stronger. And at higher temperature, the solubility of hydrogen bond groups in the hydrogel is enhanced, so that the overall healing efficiency of the gel is improved at a healing temperature of 60 ℃. That is, the hydrophobic association and reversible hydrogen bonding ensure better self-healing performance. With further increase of temperature, the healing rate of the gel is not changed, and the too high temperature possibly reduces hydrophobic association and hydrogen bonding in the system.
TABLE 1 healing Capacity of gels at different temperatures
Example 5
The hydrogel prepared in example 1 was formed into a sheet of 10mm X2 mm, and its conductivity sigma was measured using a Ningborrelica Instrument Co., ltd. FT-340 four-point probe resistivity tester.
The hydrogel prepared in example 1 was cut into 20mm×30mm×3mm long pieces and applied to different positions (e.g., finger, elbow, knee, wrist) of a human body, and the resistance of the hydrogel sensor in the movement of the joints of the human body was measured and recorded by the che 660E electrochemical workstation of the Shanghai Chen Hua instruments, inc., and the rate of change of the resistance was calculated using formula (3):
Wherein R t represents the resistance when strain is applied, and R 0 represents the resistance of the hydrogel when no strain is applied.
The strain sensitivity coefficient calculation formula is as follows:
Wherein DeltaR/R 0 is the rate of change of electrical resistance when stretched, and ε represents the tensile strain of the gel.
In the gel, the existence of a certain content of NaCl can improve the size and stability of SDS polymeric micelles and the mechanical property of the hydrophobically associating hydrogel; on the other hand, the HP (AA-co-AM) hydrogel has a three-dimensional network structure, so that a large amount of gaps exist in the gel, and meanwhile, an ion migration channel is easy to form, so that Na + and Cl - can move freely, and excellent conductivity is provided for the gel. The conductivity test results of the hydrogels are shown in FIG. 6a, where the gel conductivity is very low when no NaCl is present, and the conductivity is significantly improved after NaCl is added, indicating that the conductivity of the hydrogels is provided by NaCl. Experimental results show that when the NaCl concentration is in the range of 0-0.7mol/L, the conductivity of the gel rises as the NaCl concentration in the system increases, and the conductivity of the gel is enhanced in a certain range because the number of freely-movable ions becomes larger. Whereas when the concentration of NaCl is higher than 0.7mol/L, the conductivity of the gel is hardly changed, and a stable state is exhibited, indicating that the cumulative ion mobility is unchanged. With further increases in ion concentration, excess carriers will form ion pairs or clusters, rather than maintaining the dissociated ions, where changes in NaCl content have less effect on the conductivity of the hydrogel. Since the gel is susceptible to phase separation instability increase when the concentration of NaCl used for preparing the HP (AA 10 -co-AM) gel exceeds 0.5mol/L under the experimental conditions, and the mechanical properties of the gel begin to be poor, the HP (AA 10 -co-AM) gel with the concentration of NaCl of 0.5mol/L is selected.
As shown in fig. 6b, the complete gel and the healed HP (AA 10 -co-AM) gel after cutting are connected to the conductive loop, both gels are gradually darkened in the stretching process, and the small bulb is gradually lightened in the releasing process of the gel to return to the original length. This is because the gel deforms during stretching, the unidirectional cross-sectional density becomes large, the degree of ion migration resistance increases, the hydrogel as an elastomer returns to its cross-sectional density during releasing, and the resistance decreases, so that the bulb brightness changes.
As shown in fig. 6c, the gel has a sensing sensitivity of gf=0.78, gf=1.34, gf=1.81 at 200% -400% strain in the range of 0% -100% strain, and a good sensing sensitivity in a wide strain range, as measured by the electrochemical workstation in combination with a universal tensile tester. Fig. 6d shows the change in resistance of the gel for different tensile strains, indicating that the gel is effective as a sensor to monitor different degrees of strain. As shown in fig. 6e, the gel resistance change was stable during repeated stretching to 300% strain. In the cyclic pulling experiment of stretching to 600%, see fig. 6f, the hysteresis curves of the gel almost coincide from the fourth cycle thanks to the excellent self-healing property of the gel, which shows that the gel is stable in performance during repeated stretching for a plurality of times and can be reused for a long period of time. Based on the mechanical properties of the gel and the stability and reproducibility of the sensing properties, the HP (AA-co-AM) series of gels can be used as strain materials for self-healing flexible sensors (FIG. 6 f).
The hydrogel has high conductivity, can be cut to be self-healed, has very stable performance in the repeated stretching process, and can be used as a flexible sensor for monitoring the human body movement. As shown in fig. 7, the hydrogel is fixed to the finger, elbow, wrist and knee joints of the human body. Signals generated by the HP (AA 10 -co-AM) hydrogels during the movement of the different joints were collected by an electrochemical workstation. Experimental results show that the hydrogel strain sensor shows good signal change for bending of different parts of limbs, and the resistance change generated by gel is different in the repeated motion process of different joints of a human body. As shown in FIG. 7a, the resistance change curves generated when stretching the finger at different speeds are different, which further demonstrates the feasibility of HP (AA-co-AM) hydrogel as a strain sensor, making it an ideal material for monitoring human health and movement.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the self-healing gel based on the dynamic non-covalent bond effect is characterized by mainly comprising the following steps:
(1) Adding sodium dodecyl sulfate and NaCl into water according to the mass ratio of 5:1-1:5 to prepare micelle solution, wherein the concentration of NaCl in the micelle solution is 10-100 g/L;
(2) Adding octadecyl methacrylate into the micelle solution prepared in the step (1) to prepare a transparent solution, wherein the concentration of the octadecyl methacrylate in the transparent solution is 0.5-50 g/L;
(3) Adding acrylamide, acrylic acid and a photoinitiator into the transparent solution prepared in the step (2) to prepare a uniform solution, wherein the mass ratio of the octadecyl methacrylate to the acrylamide to the acrylic acid in the uniform solution is 1-10:100:1-15;
(4) And (3) injecting the uniform solution prepared in the step (3) into a mould, and initiating a reaction by ultraviolet light to obtain the self-healing gel with dynamic non-covalent bond effect.
2. The preparation method according to claim 1, wherein the mass ratio of the sodium dodecyl sulfate to the NaCl in the step (1) is 3:1-1:1.
3. The method according to claim 1, wherein the concentration of octadecyl methacrylate in the transparent solution in the step (2) is 1 to 20g/L.
4. The preparation method according to claim 1, wherein the mass ratio of the octadecyl methacrylate, the acrylamide and the acrylic acid in the step (3) is 1-8:100:5-15.
5. The method according to claim 1, wherein the photoinitiator in the step (3) is I2959, and the amount of the added I2959 is 0.1 to 5% of the total mole of stearyl methacrylate, acrylamide and acrylic acid.
6. The process according to claim 1, wherein the reaction time in step (4) is 1 to 10 hours.
7. The method according to claim 1, wherein the ultraviolet light in the step (4) has a wavelength of 360 to 370nm.
8. A self-healing gel prepared by the method of any one of claims 1 to 7.
9. Use of the self-healing gel of claim 8 for the preparation of flexible sensors.
10. The use of claim 9, wherein the flexible sensor is used in a wearable electronic device.
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