Polyelectrolyte gel, preparation method therefor and use thereof

Abstract

The present disclosure provides a polyelectrolyte gel, a preparation method therefor and a use thereof. Raw materials comprise a polyelectrolyte monomer and a solvent; the polyelectrolyte monomer has a solvophilic ionic group and a solvophobic and flexible nonionic group; and by adjusting the polarity of the solvent and the content of the solvent, polyelectrolyte chains undergo inhomogeneous solvation under the antagonism and balance of a long-range electrostatic interaction and a short-range solvophobic interaction, so that the polyelectrolyte forms a beaded structure. The preparation method for the polyelectrolyte gel comprises: curing and molding uniformly dispersed mixed raw materials to obtain the polyelectrolyte gel. The polyelectrolyte gel can be applied to soft robots, biomedicine, medical cosmetology, flexible wearable devices and ultrahigh-resolution printing.

Description

Polyelectrolyte gel and its preparation method and application

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on the Chinese patent application with application number 202310715758.2 and application date of June 16, 2023, and claims the priority of the Chinese patent application. The entire content of the Chinese patent application is hereby introduced into this application as a reference. Technical Field

[0003] The present disclosure belongs to the technical field of functional gels, and in particular relates to a polyelectrolyte gel and a preparation method and application thereof. Background Art

[0004] Gels are formed by swelling of a cross-linked polymer network in solvent molecules. The elasticity of the gel generally comes from the reversible conformational changes of the polymer chains between chemical cross-linking points. The free-link chain model considers the chain segments between chemical cross-linking points as N links of equal length, with a maximum uniaxial stretch ratio λ max Follow λ max ~N 1 / 2 (J.Mech.Phys.Solids 41,389-412(1993)), the maximum reversible deformation is usually lower than λ due to the uneven cross-linking of the gel network max . Generally, limited by the number N of chain segments between cross-linking points in the gel network, the elastic strain range of the gel is usually no more than 7 times. Recently, Ito et al. developed a non-fixed cross-linking sliding ring cross-linking strategy, using sliding rotaxanes on the chain to pull the originally transversely oriented chain segments to obtain more longitudinal stretching gains, thereby increasing the uniaxial elastic deformation limit to 1,000% (Science 372,1078-1081(2021)). However, biaxial elastic deformation faces greater challenges because the segments extend in two directions and covalent cross-linking severely limits the deformation capacity under biaxial stretching. The maximum linear strain under equal biaxial stretching fracture is at least 30% lower than that under uniaxial stretching (Trans.Soc.Rheol.15,91-110(1971)), not to mention reversible biaxial surface strain. To date, elastic gels with reversible biaxial surface strain greater than 2,500% have not been reported.

[0005] The beaded structure was first observed as a chain conformation in low-concentration hydrophobic polyelectrolyte aqueous solutions, as shown in Figure 1. Under the antagonism and balance of long-range electrostatic interactions and short-range hydrophobic interactions, the polyelectrolyte chains undergo uneven solvation. Polyelectrolytes containing hydrophilic and hydrophobic groups can form a beaded structure, with highly hydrated "strings" connecting less hydrated "beads." In Figure 1, l0 is the length of the "string," and D is the length of the "string." bis the diameter of the bead. The mean square radius of rotation of the bead R g Follow R g ~m b 1 / 3 , m b is the number of monomers in the bead, so the maximum stretching ratio of the bead is max (The maximum stretch ratio is defined as the mean square radius of gyration R of the fully extended polymer chain and the initial bead g The ratio between max ~m b 2 / 3 (Prog. Polym. Sci 30, 1049-1118 (2005)). Therefore, compared with the freely connected chain model at the same N value, the reversible beaded chain conformation can exhibit a higher degree of contraction and more releasable entropy, thereby achieving greater elastic deformation. However, there are currently no reports on the technology of incorporating the beaded chain structure into the gel network structure.

[0006] Summary of the Invention

[0007] The present disclosure aims to solve one of the technical problems in the related art at least to a certain extent.

[0008] In order to overcome the above-mentioned technical problems, the present disclosure provides a polyelectrolyte gel and a preparation method and application thereof, and characterizes the structure and properties of the polyelectrolyte gel.

[0009] The first aspect of the present disclosure provides a polyelectrolyte gel, the raw materials of which include polyelectrolyte monomers and a solvent, wherein the polyelectrolyte monomers have solvent-philic ionic groups and solvent-phobic and flexible non-ionic groups. By adjusting the solvent polarity and solvent content, the polyelectrolyte chains undergo uneven solvation under the antagonism and balance of long-range electrostatic interactions and short-range solvent-phobic interactions, so that the polyelectrolyte forms a beaded structure.

[0010] In some embodiments, the solvent is hydrophilic and is a mixture of any one or more of water, ethylene glycol, and glycerol.

[0011] In some embodiments, in the monomer of the polyelectrolyte, the solvophilic ionic group is a water-soluble ionic group, and the solvophobic and flexible non-ionic group is a polyethylene glycol chain, a carbon chain, or a siloxane chain.

[0012] In some embodiments, the polyelectrolyte has the structural formula -[CH2CH(COOR)] n -, [CH2C(CH3)(COOR)] n -, -[CH2CH(CONHR)] n-, -[CH2C(CH3)(CONHR)] n -, -[CH2CHR] n -, -[CH2CHR-O] n -, -[CHRCH2-O] n -、-[Si(CH3)(R)-O-(B) b ] n -、-[SiR2-O-(B) b ] n -、-[Si(CH3)(OR)-O-(B) b ] n -and-[Si(OR)2-O-(B) b ] n - any one of, n is the degree of polymerization, n ≧ 2, (B) b -[CH2CH2O] b -, b≥0, R is any one or more of the following ion-containing organic side chains and it is required that no coagulation occurs between the selected multiple ion-containing organic side chains:

[0013] R consists of polycationic segment-(M) m -A1 + -(L) l (CH3) k and free counter ion B1 - Composition, M is -CH2- or -CH2CH2O-, L can be -CH2- or -CH2CH2O-, m, l, k are the number of repeating units, 1≤m≤5, 0≤l≤5, 0≤k≤1; A1 + is an organic cation, including quaternary ammonium salts, quaternary phosphonium salts, imidazole and pyridinium cations; B1 - are anions, including fluoride, chloride, bromide, iodine, phosphate, sulfonate, carboxylate, and sulfate;

[0014] R consists of polyanion segment-(P) p -B2 - -(Q) q (CH3) r and the free counter ion is A2 + P can be -CH2- or -CH2CH2O-, Q can be -CH2- or -CH2CH2O-, p, q, r are the number of repeating units, 1≤p≤5, 0≤q≤5, 0≤r≤1; A2 + is a metal or organic cation, including lithium, sodium, potassium, magnesium, calcium, barium, zinc, silver, iron, aluminum, copper, quaternary ammonium salts, quaternary phosphonium salts, imidazolium and pyridinium cations; B2 - are anions, including sulfonate, carboxylate, phosphate, and sulfate;

[0015] R is a polyzwitterionic segment-(X) x -A3 + -(Y) y -B3 - -(Z) z (CH3) w or -(X) x -B3 - -(Y) y -A3 + -(Z) z (CH3) w , X is -CH2- or -CH2CH2O-, Y is -CH2- or -CH2CH2O-, Z is -CH2- or -CH2CH2O-, x, y, z, w are all repeating unit numbers, 1≤x≤5, 1≤y≤5, 0≤z≤5, 0≤w≤1; A3 + is an organic cation, including quaternary ammonium salts, quaternary phosphonium salts, imidazole and pyridinium cations; B3 - Anions include sulfonate, carboxylate, phosphate and sulfate.

[0016] In some embodiments, the polyelectrolyte is selected from any one or more of the following electrolyte monomers that do not coagulate with each other: (2-acryloyloxyethyl)trimethylammonium chloride, (2-acryloyloxyethyl)trimethylammonium bromide, (2-acryloyloxyethyl)trimethylammonium iodide, (3-acryloyloxypropyl)trimethylammonium chloride, (3-acryloyloxypropyl)trimethylammonium bromide, (3-acryloyloxypropyl)trimethylammonium iodide, (2-acryloyloxybutyl)trimethylammonium chloride, (2-acryloyloxybutyl)trimethylammonium bromide, (2-acryloyloxybutyl)trimethylammonium iodide, (3-acrylamidopropyl)trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium bromide, (3-acrylamidopropyl)trimethylammonium iodide, (2-acrylamidobutyl)trimethylammonium chloride, (2-acrylamidobutyl)trimethylammonium bromide, (2-acrylamidobutyl)trimethylammonium iodide, (5- Acrylamidopentyl)trimethylammonium chloride, (5-acrylamidopentyl)trimethylammonium bromide, (5-acrylamidopentyl)trimethylammonium iodide, 3-sulfopropyl acrylate potassium salt, 3-sulfopropyl acrylate sodium salt, 3-sulfopropyl acrylate lithium salt, 2-sulfoethyl acrylate sodium salt, 2-sulfoethyl acrylate potassium salt, 2-sulfoethyl acrylate lithium salt, 4-sulfobutyl acrylate potassium salt, 4-sulfobutyl acrylate sodium salt, 4-sulfobutyl acrylate lithium salt, acrylamide acrylamide 2-sulfoethyl ester sodium salt, acrylamide 2-sulfoethyl ester potassium salt, acrylamide 2-sulfoethyl ester lithium salt, acrylamide 3-sulfopropyl ester potassium salt, acrylamide 3-sulfopropyl ester sodium salt, acrylamide 3-sulfopropyl ester lithium salt, acrylamide 4-sulfobutyl ester potassium salt, acrylamide 4-sulfobutyl ester sodium salt, acrylamide 4-sulfobutyl ester lithium salt, acryloyloxyethyl sulfobetaine, acryloyloxyethyl dimethylammonium propionate, acrylamidopropyl dimethylammonium acetate and acryloyloxyethyl phosphorylcholine.

[0017] In some embodiments, the polyelectrolyte gel is prepared by free radical polymerization of a uniform mixed solution of an electrolyte monomer containing ethylene double bonds, or a siloxane electrolyte, or a polyethylene glycol electrolyte, a solvent, and an initiator under ultraviolet light or heating.

[0018] In some embodiments, the raw materials of the polyelectrolyte gel further include an initiator, and the initiator is a photoinitiator selected from at least one of 2-hydroxy-2-methylpropanedione, 2-oxoglutaric acid, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide, trifluoromethanesulfonyl ester, triethylphosphonic acid diphenyloxadiazole and diphenylethylenediamine; or the initiator is a thermal initiator selected from at least one of ammonium persulfate, potassium persulfate, sodium persulfate and ditoluyl peroxide.

[0019] In some embodiments, the raw materials for the polyelectrolyte gel further include a chemical crosslinker, selected from at least one of polyethylene glycol diacrylate, (octahydro-4,7-methylene-1H-indene-1,5-ylidene)bis(methylene) diacrylate, N,N-methylenebisacrylamide, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, vinyloxy polyethylene glycol (meth)acrylate, and 6,6'-bisamino-3,3'-methylenedibenzoic acid. In some embodiments, the chemical crosslinker is present in an amount of 0-0.01 equivalents relative to the polyelectrolyte monomer. In some embodiments, the polyelectrolyte chains undergo heterogeneous solvation in the solution system prior to gel formation, with the molar ratio of polyelectrolyte monomer to solvent molecules ranging from 1:2.5 to 1:12.

[0020] In some embodiments, the molar ratio of the polyelectrolyte monomer to the solvent molecules is between 1:3 and 1:8.

[0021] In some embodiments, the polyelectrolyte gel is isotropic and has a reversible uniaxial strain of 700% to 1500% and a reversible biaxial strain of 3000% to 10,000%.

[0022] In some embodiments, the strain of the polyelectrolyte gel after 5 minutes of repair reaches 20% of the initial strain. Therefore, the polyelectrolyte gel provided by the present application has repair properties.

[0023] The present disclosure provides a polyelectrolyte having solvophilic ionic groups and solvophobic and flexible nonionic groups. By adjusting the solvent content, the chain conformation can be conveniently regulated. When the solvent molecules are insufficient to completely solvate all polyelectrolyte chains, the solvophobic interactions between the nonionic groups begin to compete with the electrostatic interactions between the ionic groups on the chains. The flexible polymer chains collapse into a beaded conformation, with highly solvated "strings" connecting less solvated "beads," thereby minimizing contact between the nonionic groups and solvent molecules and maximizing contact between the ionic groups and solvent molecules.

[0024] The high content of polyelectrolyte monomers in the polyelectrolyte gel provided by the present invention easily forms tight interchain entanglements, forming a physical cross-linked network. Within a certain range, no matter how large the uniaxial or biaxial strain is applied, the rigid interchain entanglement remains intact to provide physical cross-linking; if the content of polyelectrolyte chains is not enough to form tight interchain physical entanglements, chemical cross-linking can be provided by adding 0-0.01 equivalents of chemical cross-linking agents relative to the polyelectrolyte monomers. When the material is subjected to sufficient strain, the beaded conformation in the polyelectrolyte gel can be continuously unfolded to increase the polymer chains between the cross-linking points and toughen the polyelectrolyte gel. After the stress is removed, the chain segments can reversibly return to the initial beaded conformation. In addition, the reversible stretching process does not involve the breaking of irreversible chemical bonds, and the non-directional electrostatic interaction can fully restore the beaded structure, giving the material mechanical properties that do not decay after repeated tensile tests.

[0025] A second aspect of the present disclosure provides a method for preparing a polyelectrolyte gel, comprising the following steps:

[0026] The polyelectrolyte monomer, solvent, initiator and optional cross-linking agent are mixed and stirred at room temperature to uniformly disperse them to obtain a uniform dispersion.

[0027] The uniform dispersion is solidified and formed to obtain the polyelectrolyte gel.

[0028] In some embodiments, the uniform dispersion is cured by ultraviolet light or heating at a temperature of 25±3° C. and a humidity of 30±15%.

[0029] In some embodiments, the initiator is a photoinitiator selected from at least one of 2-hydroxy-2-methylpropanedione, 2-oxoglutaric acid, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, trifluoromethanesulfonyl ester, triethylphosphonic acid diphenyloxadiazole and diphenylethylenediamine; or the initiator is a thermal initiator selected from at least one of ammonium persulfate, potassium persulfate, sodium persulfate and ditoluyl peroxide.

[0030] In some embodiments, the cross-linking agent is at least one of polyethylene glycol diacrylate, (octahydro-4,7-methylene-1H-indene-1,5-ylidene)bis(methylene)diacrylate, N,N-methylenebisacrylamide, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethyleneoxy (meth)acrylate, and 6,6'-bisamino-3,3'-methylenedibenzoic acid.

[0031] The preparation method of the polyelectrolyte gel provided by the present disclosure adopts a one-step polymerization method, which has a simple preparation process, cheap and readily available raw materials, mild reaction conditions, low preparation cost, and is easy to scale up production.

[0032] A third aspect of the present disclosure provides an application of a polyelectrolyte gel in soft robotics, biomedicine, medical cosmetology, flexible wearable devices, and ultra-high-resolution printing.

[0033] The polyelectrolyte gel provided by the present disclosure has excellent mechanical strength, elasticity, ionic conductivity, rapid repair performance and biocompatibility. The above-mentioned polyelectrolyte gel can be applied to related fields such as soft robotics, biomedicine, medical cosmetology, flexible wearable devices and ultra-high-resolution printing. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] FIG1 is a schematic diagram of a disclosed beaded structure;

[0035] FIG2 is an AFM height image of a superelastic ion-conducting gel;

[0036] FIG3 is a true stress-strain curve of polyelectrolyte gels with different water contents;

[0037] FIG4 is a true stress-strain curve of cyclic stretching of a superelastic ion conductive gel;

[0038] FIG5 is a cyclic compression stress-strain curve of a superelastic ion conductive gel;

[0039] FIG6 is a rheological test showing that the storage modulus and loss modulus of the superelastic ion conductive gel vary with frequency;

[0040] FIG7 a is a biaxial elastic diagram of an aerodynamic model made of a superelastic ion-conductive gel, and FIG7 b is a finite element simulation diagram of an aerodynamic model made of a superelastic ion-conductive gel after inflation;

[0041] FIG8 is a test of the rapid repair performance of the superelastic ion conductive gel;

[0042] FIG9 is a test of the ionic conductivity of the superelastic ion conductive gel before and after rapid repair;

[0043] FIG10 is a pneumatic model made of superelastic ion conductive gel to realize self-volume sensing;

[0044] FIG11 is an impact test of an aerodynamic model made of superelastic ion conductive gel. DETAILED DESCRIPTION

[0045] In order to make the purpose, technical solutions and advantages of the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are merely used to explain the present application and are not intended to limit the present application. On the contrary, the present application covers any substitutions, modifications, equivalent methods and solutions made on the spirit and scope of the present application as defined by the claims. Furthermore, in order to provide the public with a better understanding of the present application, some specific details are described in detail in the detailed description of the present application below. Those skilled in the art can fully understand the present application without the description of these details.

[0046] The present disclosure provides a superelastic and rapidly repairable polyelectrolyte gel with ultra-large reversible biaxial surface strain. The polyelectrolyte gel has a beaded structure and comprises a polyelectrolyte and a solvent. The monomers of the polyelectrolyte have solvent-philic ionic groups and solvent-phobic and flexible non-ionic groups. By adjusting the solvent polarity and solvent content, the polyelectrolyte chains undergo uneven solvation under the antagonism and balance of long-range electrostatic interactions and short-range solvent-phobic interactions, so that the polyelectrolyte forms a beaded structure, in which highly solvated "strings" connect "beads" with lower solvation levels.

[0047] The first aspect of the present disclosure provides a polyelectrolyte gel, which uses polyelectrolytes having solvophilic ionic groups and solvophobic and flexible nonionic groups. By adjusting the solvent content, the conformation of the polyelectrolyte chains can be conveniently controlled. When the solvent molecules are insufficient to completely solvate all the polyelectrolyte chains, the solvophobic interaction between the nonionic groups begins to compete with the electrostatic interaction between the ionic groups on the chains, and the flexible polymer chains collapse into a beaded structure. The highly solvated "strings" (meaning that in the solution, the solute is completely surrounded by solvent molecules, and there are no ions free outside the molecular surroundings) connect the less solvated "beads", thereby minimizing the contact between the nonionic groups and the solvent molecules and maximizing the contact between the ionic groups and the solvent molecules.

[0048] High polyelectrolyte content in the gel readily forms tight interchain physical entanglements, forming the crosslinking points of the elastic network. Within a certain range, the rigid interchain entanglements remain intact, providing physical crosslinks, regardless of the application of large uniaxial or biaxial strains. If the polyelectrolyte chain content is insufficient to form tight interchain physical entanglements, chemical crosslinking points can be provided by adding 0-0.01 equivalents of a chemical crosslinker relative to the polyelectrolyte monomer. When sufficient strain is applied to the material, the beaded structure between the crosslinking points not only straightens the strings on the chains, but also extends the length of the polymer chains between the crosslinking points by pulling out from the beads. Furthermore, thanks to the low energy state and entropic drive of the beaded structure, the chain segments can quickly and reversibly return to the initial beaded conformation after stress removal, thereby significantly increasing the reversible strain range of the material. Furthermore, the stretching process does not involve irreversible breaking of chemical bonds, and non-directional electrostatic interactions can fully recover the beaded structure, endowing the material with mechanical properties that do not decay after repeated tensile testing. In addition, the flexible chain segments and the large number of electrostatic interactions endow the gel with rapid repair properties, and the intrinsic ionic properties of the material lay the foundation for self-sensing.

[0049] The second aspect of the present disclosure is to provide a method for preparing a polyelectrolyte gel, comprising the following steps:

[0050] (1) A certain molar amount of polyelectrolyte monomer, a solvent equivalent to 2.5-12 equivalents of the polyelectrolyte monomer, an initiator equivalent to 0.00002-0.01 equivalents of the polyelectrolyte monomer, and a chemical cross-linking agent equivalent to 0-0.01 equivalents of the polyelectrolyte monomer are mixed and stirred at room temperature to obtain a uniform dispersion (in the uniform dispersion, the molar fraction of the polyelectrolyte monomer is 7.7% to 28.6%, and the molar fraction of the solvent molecules is 71.4% to 92.3%).

[0051] (2) pouring the uniform dispersion obtained in step (1) into a mold, and curing the mold by ultraviolet light or heating at a temperature of 25±3° C. and a humidity of 30±15% to obtain a polyelectrolyte gel.

[0052] The monomers of the polyelectrolyte used in the following examples are: (2-acryloyloxyethyl)trimethylammonium chloride (hereinafter abbreviated as AETC, 80 wt% in H2O), 3-sulfopropyl acrylate potassium salt (hereinafter abbreviated as PSK, 98 wt%), acryloyloxyethyl sulfobetaine (hereinafter abbreviated as BA), photoinitiator: 2-hydroxy-2-methylpropanedione (hereinafter abbreviated as HMPP, 98 wt%), thermal initiator: benzoyl peroxide (hereinafter abbreviated as BPO, 98 wt%) and chemical crosslinker: polyethylene glycol diacrylate (hereinafter abbreviated as PEGDA 400, 98 wt%), the solvents are water, ethylene glycol and glycerol; except BA, the remaining reagents can be purchased from Energy Chemical.

[0053] Acryloyloxyethyl sulfobetaine (hereinafter referred to as BA) is prepared by the following steps:

[0054] 0.05 mol of 1,3-propane sultone and 10 g of acetonitrile were mixed evenly and then added to a mixture of 0.05 mol of dimethylaminoethyl acrylate and 10 g of acetonitrile. The mixture was stirred at 25°C for 12 h and then allowed to stand for 36 h. The resulting white precipitate was repeatedly filtered, centrifuged, and rinsed with acetonitrile and acetone to obtain powdered acryloyloxyethyl sulfobetaine (BA).

[0055] In this application, the microstructure of the polyelectrolyte gel was characterized using atomic force microscopy (AFM); the mechanical, elastic, and rapid-healing properties of the polyelectrolyte gel were characterized using a tensile tester; the rheological properties of the polyelectrolyte gel were characterized using a dynamic rheometer; and the ionic conductivity and sensing properties of the polyelectrolyte gel were characterized using electrochemical impedance spectroscopy (EIS). These performance testing procedures are detailed in the various examples provided below.

[0056] Examples 1-13 are used to illustrate the preparation method of polyelectrolyte gel

[0057] Example 1. Polyelectrolyte AETC hydrogel (20 wt% H2O, -[CH2CH(COO(CH2)2N + (CH3)3)] n -nCl - ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:2.69, comprising the following steps:

[0058] (1) 20 mmol of AETC (containing 53.8 mmol of water) and 0.0013 mmol of photoinitiator HMPP were mixed and stirred for 3 hours to obtain a uniform dispersion.

[0059] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) are irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0060] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0061] Example 2, polyelectrolyte AETC hydrogel (25wt% H2O, -[CH2CH(COO(CH2)2N + (CH3)3)] n -nCl - ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:3.59, comprising the following steps:

[0062] (1) 20 mmol of AETC (containing 53.8 mmol of water) was added to 18 mmol of deionized water and 0.0013 mmol of photoinitiator HMPP, and the mixture was stirred for 3 hours to obtain a uniform dispersion.

[0063] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) are irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0064] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0065] Example 3, polyelectrolyte AETC hydrogel (30wt% H2O, -[CH2CH(COO(CH2)2N + (CH3)3)] n -nCl - ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:4.61, comprising the following steps:

[0066] (1) 20 mmol of AETC (containing 53.8 mmol of water) was added to 38.4 mmol of deionized water and 0.0013 mmol of photoinitiator HMPP, and the mixture was stirred for 3 hours to obtain a uniform dispersion.

[0067] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm between the ultraviolet lamp tube and the sample) are irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0068] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0069] Example 4: Polyelectrolyte AETC hydrogel (35 wt% H2O, -[CH2CH(COO(CH2)2N + (CH3)3)] n -nCl - ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:5.8, comprising the following steps:

[0070] (1) 20 mmol of AETC (containing 53.8 mmol of water), 62.1 mmol of deionized water, and 0.0013 mmol of photoinitiator HMPP were added and stirred for 3 hours to obtain a uniform dispersion.

[0071] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) was poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays were generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) were irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0072] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0073] Example 5, Polyelectrolyte AETC Hydrogel (30wt% H2O, -[CH2CH(COO(CH2)2N + (CH3)3)] n -nCl - ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:4.61, comprising the following steps:

[0074] (1) 20 mmol of AETC (containing 53.8 mmol of water), 18 mmol of deionized water, and 0.0066 mmol of photoinitiator HMPP were added and stirred for 3 hours to obtain a uniform dispersion.

[0075] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) are irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0076] Alternatively, for a sample for compression testing, the solution in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0077] Example 6, chemical cross-linked polyelectrolyte AETC hydrogel (30wt% H2O, -[CH2CH(COO(CH2)2N + (CH3)3)] n -nCl - ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:4.61, comprising the following steps:

[0078] (1) 20 mmol of AETC (containing 53.8 mmol of water) was added to 62.1 mmol of deionized water, 0.0013 mmol of photoinitiator HMPP, and 0.00013 mmol of crosslinker PEGDA400, and the mixture was stirred for 3 hours to obtain a uniform dispersion.

[0079] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) are irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0080] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0081] Example 7, chemical cross-linked polyelectrolyte AETC hydrogel (30wt% H2O, -[CH2CH(COO(CH2)2N + (CH3)3)] n -nCl - ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:4.61, comprising the following steps:

[0082] (1) 20 mmol AETC (containing 53.8 mmol water), 62.1 mmol deionized water, 0.0018 mmol photoinitiator HMPP, and 0.0056 mmol crosslinker PEGDA400 were mixed and stirred for 3 hours to obtain a uniform dispersion.

[0083] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) are irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0084] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0085] Example 8, polyelectrolyte PSK hydrogel (30wt% H2O, -[CH2CH(COO(CH2)3SO3 - )] n -nK + ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:5.53, comprising the following steps:

[0086] (1) 20 mmol of PSK, 110.6 mmol of deionized water, and 0.0018 mmol of photoinitiator HMPP were mixed and stirred for 3 hours to obtain a uniform dispersion.

[0087] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) are irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0088] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0089] Example 9, chemical cross-linked polyelectrolyte PSK hydrogel (40wt% H2O, -[CH2CH(COO(CH2)3SO3 - )] n -nK + ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:8.6, comprising the following steps:

[0090] (1) 20 mmol of PSK, 172.1 mmol of deionized water, 0.0018 mmol of photoinitiator HMPP, and 0.0013 mmol of crosslinker PEGDA400 were mixed and stirred for 3 hours to obtain a uniform dispersion.

[0091] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) are irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0092] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0093] Example 10, Polyelectrolyte BA Hydrogel (30wt% H2O, -[CH2CH(COO(CH2)2N + (CH3)2(CH2)3SO3 - )] n -nK + ), wherein the molar ratio of the polyelectrolyte monomer to water is 1:6.36, comprising the following steps:

[0094] (1) 20 mmol BA, 127.3 mmol deionized water, 0.002 mmol photoinitiator HMPP and 0.002 mmol crosslinker PEGDA400 were mixed and stirred for 3 hours to obtain a uniform dispersion.

[0095] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) was poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize water volatilization. Subsequently, ultraviolet rays (the ultraviolet rays were generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) were irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0096] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0097] Example 11, chemical cross-linked polyelectrolyte BA glycol gel (70wt% CH2OHCH2OH, -[CH2CH(COO(CH2)2N + (CH3)2(CH2)3SO3 - )] n -nK + ), wherein the molar ratio of the polyelectrolyte monomer to the ethylene glycol is 1:10.05, comprising the following steps:

[0098] (1) 20 mmol of BA, 201 mmol of ethylene glycol, 0.003 mmol of thermal initiator BPO, and 0.002 mmol of crosslinker PEGDA400 were mixed and stirred for 3 hours to obtain a uniform dispersion.

[0099] (2) For the sample to be used for tensile testing, pour the uniform dispersion obtained in step (1) into a dumbbell-shaped polytetrafluoroethylene mold and cover it with a transparent square plastic Petri dish to minimize evaporation. Subsequently, heat it at a temperature of 60±20°C for 10 min-24 h to obtain a barbell-shaped tensile specimen with a main body size of 20 mm × 10 mm × 2.5±0.1 mm (length × width × thickness).

[0100] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0101] Example 12, chemically cross-linked polyelectrolyte BA glycol gel (70 wt% CH2OHCH2OH, -[CH2CH(COO(CH2)2N + (CH3)2(CH2)3SO3 - )] n -nK + ), wherein the molar ratio of the polyelectrolyte monomer to the ethylene glycol is 1:10.05, comprising the following steps:

[0102] (1) 20 mmol BA, 201 mmol ethylene glycol, 0.003 mmol photoinitiator HMPP, and 0.001 mmol crosslinker PEGDA400 were mixed and stirred for 3 hours to obtain a uniform dispersion.

[0103] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize volatilization. Subsequently, ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) are irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0104] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0105] Example 13, chemically cross-linked polyelectrolyte BA glycerol gel (80wt% CH2OHCHOHCH2OH, -[CH2CH(COO(CH2)2N + (CH3)2(CH2)3SO3 - )] n -nK + ), wherein the molar ratio of the polyelectrolyte monomer to the glycerol is 1:11.6, comprising the following steps:

[0106] (1) 20 mmol of BA, 232 mmol of glycerol, 0.003 mmol of photoinitiator HMPP, and 0.002 mmol of crosslinker PEGDA400 were mixed and stirred for 3 hours to obtain a uniform dispersion.

[0107] (2) For the sample to be used for tensile testing, the uniform dispersion obtained in step (1) was poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic petri dish to minimize volatilization. Subsequently, ultraviolet light (the ultraviolet light was generated by an ultraviolet lamp with a lamp tube wavelength of 200nm to 420nm, a power of 36W, and a distance of 6cm from the sample) was irradiated for 10min to 60min at a temperature of 25±3°C and a humidity of 30±15% to obtain a barbell-shaped tensile specimen with a main body size of 20mm×10mm×2.5±0.1mm (length×width×thickness).

[0108] Alternatively, for samples for compression testing, the uniform dispersion obtained in step (1) is poured into a cylindrical mold and irradiated with ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm to 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) for 20min to obtain a cylindrical compression specimen with a diameter of 10mm and a height of 10mm.

[0109] The effectiveness of the embodiment of the present disclosure is verified as follows:

[0110] 1. Structural Characterization of Polyelectrolyte Gels

[0111] Analysis example 1

[0112] (1) Use double-sided tape to stick the mica sheet to the iron sheet, and then use frosted tape to peel off the mica sheet to get a clean and flat surface.

[0113] (2) Cut 2 mg of the sample in Example 2 (containing 25 wt% water) and immerse it in 1 ml of deionized water, stirring thoroughly.

[0114] (3) Next, 10 μL of the polyelectrolyte aqueous solution (1.5 mg / mL) in (2) was taken out with a pipette and dropped onto the mica sheet.

[0115] (4) Wait 10 minutes until the water evaporates to the point where no visible water is visible to the naked eye, and then take an AFM height image, as shown in Figure 2. In the AFM height image, the bright spheres indicated by the letter A correspond to the beads in the beaded structure, and the narrow and thin bright lines indicated by the letter B correspond to the strings in the beaded structure. The beaded structure is a structure in which the beads are connected by strings, corresponding to the polymer chains partially collapsing into spherical conformations under the balance of electrostatic and hydrophobic interactions, and the spherical conformations are connected by linear polymer chains.

[0116] 2. Mechanical Properties of Polyelectrolyte Gels

[0117] Analysis example 2

[0118] (1) A uniaxial tensile test was performed on a barbell-shaped tensile specimen with a main body size of 20 mm × 10 mm × 2.5 ± 0.1 mm (length × width × thickness) in Example 2 under the conditions of a temperature of 25 ± 3°C and a humidity of 30 ± 15%.

[0119] (2) The two ends of the sample are bonded with a thick piece of material and clamped with a tensile testing machine to reduce slippage. The initial length between the clamps is 10 ± 1 mm.

[0120] (3) Unless otherwise stated, all tensile tests were performed at 100 mm min. -1The cyclic tensile test was performed at a loading rate of 1.000. The clamps were loosened between loading cycles, allowing the specimen to be subjected to zero force and a relaxation time of 1 minute. Each curve was repeated for at least three independent samples.

[0121] (4) The tensile curves of the polyelectrolyte gels prepared under different conditions are shown in FIG3 (the mass fraction of water in the polyelectrolyte gel is 20 wt%, 25 wt%, 30 wt%, and 35 wt%, respectively), corresponding to the samples in Example 1, Example 2, Example 3, and Example 4, respectively. It should be noted that the nominal stress is equal to the force divided by the initial cross-sectional area of ​​the material. Since the materials of the disclosed embodiments have high tensile properties and the cross-sectional area changes greatly, it is inevitable that there will be a certain data deviation from the nominal stress generated during the loading process. The true stress assumes that the material volume is conserved and takes the change of the cross-sectional area into account, satisfying the following relationship: true stress = nominal stress × (strain / 100 + 1), the unit of strain is %, and a stretch of 1 times the strain is 100%. Therefore, the use of the true stress can better reflect the tensile condition of the material.

[0122] (5) At a water mass fraction of 25 wt%, the resulting polyelectrolyte gel exhibits excellent tensile properties, mechanical strength, and elastic properties. It can be uniaxially stretched to 3000% of its original length before breaking, and can withstand a maximum uniaxial true stress of approximately 11.5 MPa. The cyclic stress-strain curves for four uniaxial strains of 1500% are essentially identical, demonstrating a fully reversible uniaxial elastic deformation of up to 15 times (see Figure 4).

[0123] Analysis example 3

[0124] (1) A compressive stress-strain test was performed on the cylindrical specimen with a diameter of 10 mm and a height of 10 mm in Example 2 at a temperature of 25±3°C and a humidity of 30±15%.

[0125] (2) Unless otherwise specified, the cyclic compression stress-strain curves are based on a loading rate of 500 mm min -1 The relaxation time between cycles was 1 s. Each curve was repeated for at least three independent samples.

[0126] (3) The obtained polyelectrolyte gel has excellent compressive elastic properties. The compressive stress-strain curve with a compressive strain of 60% after 1000 cycles is basically consistent with that of the first cycle, see Figure 5.

[0127] Analysis example 4

[0128] (1) The storage modulus (G') and loss modulus (G") of the polyelectrolyte gel in Example 2 were measured using a dynamic rheometer.

[0129] (2) Prepare polyelectrolyte gel discs with a thickness of 1.2 mm and a diameter of 20 mm.

[0130] (3) The applied axial force is 1 N, and the angular frequency sweep range is 0.1 to 100 rad s -1 , the shear strain is constant at 1%.

[0131] (4) As can be seen from the results in Figure 6, the storage modulus is much larger than the loss modulus, indicating that the polyelectrolyte gel is -1 The angular frequency range is all on the rubber platform.

[0132] Analysis example 5

[0133] (1) A sample of a specific shape was prepared using the uniform dispersion obtained in step (1) of Example 2, and then a cuboid pneumatic model with an internal cavity of V0 = 0.54 mL was obtained by photocuring and splicing. The external contour of the model was 23 mm × 17 mm × 6 mm in length × width × height, and the internal cavity was 15 mm × 9 mm × 4 mm in length × width × height.

[0134] (2) Use a syringe to fill 550 mL of air into the cavity in the pneumatic model (the volume of the internal cavity changes by about 1000 times), and then use a syringe to extract the air. The shape of the material can be completely restored (as shown in Figure 7a).

[0135] (3) Through Abaqus finite element simulation analysis of the process in step (2) of Example 5, as shown in Figure 7b, the reversible maximum linear strain reached 1377%, showing a recoverable biaxial elastic surface strain greater than 10,000%.

[0136] 3. Characterization of ionic conductivity and sensing properties of polyelectrolyte gels

[0137] Analysis example 6

[0138] (1) In this example, the polyelectrolyte gel prepared in Example 2 was used to perform electrochemical impedance spectroscopy (EIS), as shown in FIG8 .

[0139] (2) The polyelectrolyte gel after repair for 1 second has the same electrochemical impedance properties as that of the undamaged one, and its ionic conductivity is about 4.9 mS / cm.

[0140] Analysis example 7

[0141] (1) The uniform dispersion obtained in step (1) of Example 2 is used to prepare a sample of a specific shape, and then a gripper model is obtained by photocuring and splicing.

[0142] (2) Different volumes of gas were introduced into the gripper model, and the Rt curve was measured to calculate the change in resistance with the volume of gas introduced. As shown in FIG9 , the resistance changed significantly with the volume, indicating that the polyelectrolyte gel of this embodiment can be used as an excellent sensing material.

[0143] 4. Characterization of the rapid repair properties of polyelectrolyte gels

[0144] Analysis example 8

[0145] (1) The barbell-shaped tensile specimen in Example 2 was cut into two halves using a fresh blade and pressed manually for different periods of time at ambient temperature (24±1°C).

[0146] (2) The samples repaired at different times in (1) were fixed at 100 mm min -1 The tensile test was performed at a loading rate of 100 nm. It was found that the sample repaired for 1 minute could be stretched 2 times, and the sample repaired for 5 minutes could be stretched 6 times. The test results are shown in Figure 10.

[0147] Analysis example 9

[0148] (1) A sample of a specific shape was prepared using the uniform dispersion obtained in step (1) of Example 2, and then a rectangular pneumatic model was obtained by photocuring and splicing. The outer contour of the model was 23 mm × 17 mm × 6 mm in length × width × height, and the inner cavity was 15 mm × 9 mm × 4 mm in length × width × height.

[0149] (2) Use a syringe to fill 50 mL of air into the cavity in (1). After removing the needle, the model can quickly repair the seal.

[0150] (3) Use a needle to puncture the pneumatic model inflated in (2). After only a few seconds of repair, the pneumatic model can be inflated with 50 mL of air and remains sealed.

[0151] 5. Impact resistance of polyelectrolyte gel balloons

[0152] Analysis example 10

[0153] (1) A sample of a specific shape was prepared using the uniform dispersion obtained in step (1) of Example 2, and then a rectangular pneumatic model was obtained by photocuring and splicing. The outer contour of the model was 23 mm × 17 mm × 6 mm in length × width × height, and the inner cavity was 15 mm × 9 mm × 4 mm in length × width × height.

[0154] (2) Use a syringe to fill 50 mL of air into the cavity in (1). After removing the needle, the model can quickly repair the seal.

[0155] (3) The pneumatic model inflated in (2) was placed under a tensile testing machine for compression stress-strain testing. The model height could be compressed by 80% and withstand a pressure greater than 100N without breaking, as shown in Figure 11. It also quickly rebounded to its original shape after the external force was removed.

[0156] Analysis example 11

[0157] (1) The uniform dispersion obtained in step (1) of Example 2 was used to prepare a sample of a specific shape, and then a cubic pneumatic model was obtained by photocuring and splicing. Its outer contour was 40 mm × 40 mm × 40 mm in length × width × height, and its internal cavity was 30 mm × 30 mm × 30 mm in length × width × height.

[0158] (2) Use a syringe to fill 2700 mL of air into the cavity in (1). After removing the needle, the model can quickly repair the seal.

[0159] (3) The pneumatic model in (2) after being inflated (volume changes by about 100 times) can withstand the weight of an adult without breaking, and rebounds immediately after the external force is removed.

[0160] Industrial Applicability

[0161] The preparation method of the polyelectrolyte gel provided by the embodiment of the present disclosure is simple, and the obtained polyelectrolyte gel has excellent tensile and elastic properties; at the same time, the polyelectrolyte gel of the embodiment of the present disclosure has excellent fast repair properties, and can quickly repair various small mechanical damages, including acupuncture, cutting, etc.; the polyelectrolyte gel of the embodiment of the present disclosure also has excellent ionic conductivity, which lays the foundation for self-volume sensing and external perception; the balloon obtained based on the polyelectrolyte gel of the embodiment of the present disclosure also has excellent impact resistance. In summary, the polyelectrolyte gel of the embodiment of the present disclosure and its design concept have broad application prospects in soft robots, superelastic electrodes, drug delivery carriers, tissue engineering scaffolds, bioelectronics, wound dressings, contact lenses, batteries and supercapacitors, optical equipment, acoustic equipment, energy converters, bioadhesives, coatings, medical beauty, ultra-high resolution printing and other fields.

[0162] In addition, in the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0163] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A polyelectrolyte gel, wherein the raw materials of the polyelectrolyte gel include polyelectrolyte monomers and solvents, the polyelectrolyte monomers have solvent-philic ionic groups and solvent-phobic and flexible non-ionic groups, and by adjusting the solvent polarity and solvent content, the polyelectrolyte chains undergo uneven solvation under the antagonism and balance of long-range electrostatic interactions and short-range solvent-phobic interactions, so that the polyelectrolyte forms a beaded structure.

2. The polyelectrolyte gel according to claim 1, wherein The solvent is hydrophilic and is selected from a mixture of any one or more of water, ethylene glycol and glycerol.

3. The polyelectrolyte gel according to claim 1, wherein In the monomer of the polyelectrolyte, the solvent-philic ionic group is an ionic group that is easily soluble in water, and the solvent-phobic and flexible non-ionic group is a polyethylene glycol chain, a carbon chain or a siloxane chain.

4. The polyelectrolyte gel according to claim 1, wherein The structural formula of the polyelectrolyte is -[CH2CH(COOR)] n -, [CH2C(CH3)(COOR)] n -、-[CH2CH(CONHR)] n -, -[CH2C(CH3)(CONHR)] n -, -[CH2CHR] n -, -[CH2CHR-O] n -、-[CHRCH2-O] n -、-[Si(CH3)(R)-O-(B) b ] n -、-[SiR2-O-(B) b ] n -、-[Si(CH3)(OR)-O-(B) b ] n - and - [Si(OR)2-O-(B) b ] n - any one of the following, n is the degree of polymerization, n≧2, (B) b -[CH2CH2O] b -, b≥0, R is any one or more of the following ion-containing organic side chains and it is required that no coagulation occurs between the selected multiple ion-containing organic side chains: R consists of a polycationic segment-(M) m -A1 + -(L) l (CH3) k and free counter ion B1 - Composition, M can be -CH2- or -CH2CH2O-, L can be -CH2- or -CH2CH2O-, m, l, k are the number of repeating units, 1≤m≤5, 0≤l≤5, 0≤k≤1; A1 + is an organic cation, including quaternary ammonium salts, quaternary phosphonium salts, imidazole and pyridinium cations; B1 - are anions, including fluoride, chloride, bromide, iodine, phosphate, sulfonate, carboxylate and sulfate; R consists of polyanion segments-(P) p -B2 - -(Q) q (CH3) r and the free counter ion is A2 + P can be -CH2- or -CH2CH2O-, Q can be -CH2- or -CH2CH2O-, p, q, r are the number of repeating units, 1≤p≤5, 0≤q≤5, 0≤r≤1; A2 + is a metal or organic cation, including lithium, sodium, potassium, magnesium, calcium, barium, zinc, silver, iron, aluminum, copper, quaternary ammonium salts, quaternary phosphonium salts, imidazole and pyridinium cations; B2 - are anions, including sulfonate, carboxylate, phosphate and sulfate; R is a polyzwitterionic segment - (X) x -A3 + -(Y) y -B3 - -(Z) z (CH3) w or -(X) x -B3 - -(Y) y -A3 + -(Z) z (CH3) w , X is -CH2- or -CH2CH2O-, Y is -CH2- or -CH2CH2O-, Z is -CH2- or -CH2CH2O-, x, y, z, w are all repeating unit numbers, 1≤x≤5, 1≤y≤5, 0≤z≤5, 0≤w≤1; A3 + B3 is an organic cation, including quaternary ammonium salts, quaternary phosphonium salts, imidazole and pyridinium cations; - Anions include sulfonate, carboxylate, phosphate and sulfate.

5. The polyelectrolyte gel according to claim 1, wherein The polyelectrolyte is selected from any one or more of the following electrolyte monomers that do not coagulate with each other: (2-acryloyloxyethyl) trimethylammonium chloride, (2-acryloyloxyethyl) trimethylammonium bromide, (2-acryloyloxyethyl) trimethylammonium iodide, (3-acryloyloxypropyl) trimethylammonium chloride, (3-acryloyloxypropyl) trimethylammonium bromide, (3-acryloyloxypropyl) trimethylammonium iodide, (2-acryloyloxybutyl) trimethylammonium chloride, (2-acryloyloxybutyl) trimethylammonium bromide, (2-acryloyloxybutyl) trimethylammonium iodide, (3-acrylamidopropyl) trimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium bromide, (3-acrylamidopropyl) trimethylammonium iodide, (2-acrylamidobutyl) trimethylammonium chloride, (2-acrylamidobutyl) trimethylammonium bromide, (2-acrylamidobutyl) trimethylammonium iodide, (5 ...2-acrylamidobutyl) trimethylammonium bromide, (2-acrylamidobutyl) trimethylammonium iodide, (5-acrylamidopropyl) trimethylammonium chloride, (2-acrylamidobutyl) trimethylammonium b (5-acrylamidopentyl)trimethylammonium chloride, (5-acrylamidopentyl)trimethylammonium bromide, (5-acrylamidopentyl)trimethylammonium iodide, 3-sulfopropyl acrylate potassium salt, 3-sulfopropyl acrylate sodium salt, 3-sulfopropyl acrylate lithium salt, 2-sulfoethyl acrylate sodium salt, 2-sulfoethyl acrylate potassium salt, 2-sulfoethyl acrylate lithium salt, 4-sulfobutyl acrylate potassium salt, 4-sulfobutyl acrylate sodium salt, 4-sulfobutyl acrylate lithium salt, acrylamide 2- Sulfoethyl sodium salt, acrylamide 2-sulfoethyl ester potassium salt, acrylamide 2-sulfoethyl ester lithium salt, acrylamide 3-sulfopropyl ester potassium salt, acrylamide 3-sulfopropyl ester sodium salt, acrylamide 3-sulfopropyl ester lithium salt, acrylamide 4-sulfobutyl ester potassium salt, acrylamide 4-sulfobutyl ester sodium salt, acrylamide 4-sulfobutyl ester lithium salt, acryloyloxyethyl sulfobetaine, acryloyloxyethyl dimethylammonium propionate, acrylamidopropyl dimethylammonium acetate and acryloyloxyethyl phosphorylcholine.

6. The polyelectrolyte gel according to claim 1, wherein The polyelectrolyte gel is prepared by free radical polymerization of a uniform mixed solution of an electrolyte monomer containing ethylene double bonds or a siloxane electrolyte or a polyethylene glycol electrolyte, a solvent and an initiator under ultraviolet light or heating.

7. The polyelectrolyte gel according to claim 1, wherein The raw materials of the polyelectrolyte gel also include an initiator, which is a photoinitiator selected from at least one of 2-hydroxy-2-methylpropanedione, 2-oxoglutaric acid, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, trifluoromethanesulfonyl ester, triethylphosphonic acid diphenyloxadiazole and diphenylethylenediamine; or the initiator is a thermal initiator selected from at least one of ammonium persulfate, potassium persulfate, sodium persulfate and ditoluyl peroxide.

8. The polyelectrolyte gel according to claim 1, wherein The raw materials of the polyelectrolyte gel also include a chemical crosslinking agent, and the chemical crosslinking agent is selected from at least one of polyethylene glycol diacrylate, (octahydro-4,7-methylene-1H-indene-1,5-ylidene)bis(methylene) diacrylate, N,N-methylenebisacrylamide, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, (meth)acrylate ethyleneoxy polyethylene glycol ester and 6,6'-bisamino-3,3'-methylene dibenzoic acid.

9. The polyelectrolyte gel according to claim 8, wherein The content of the chemical cross-linking agent is 0-0.01 equivalent relative to the polyelectrolyte monomer.

10. The polyelectrolyte gel according to any one of claims 1 to 9, wherein The molar ratio of the polyelectrolyte to the solvent molecules is 1:2.5 to 1:

12.

11. The polyelectrolyte gel according to claim 10, wherein The molar ratio of the polyelectrolyte monomer to the solvent molecule is preferably between 1:3 and 1:

8.

12. The polyelectrolyte gel according to claim 10, wherein The polyelectrolyte gel is isotropic and has a reversible uniaxial strain of 700% to 1500% and a reversible biaxial surface strain of 3000% to 10,000%.

13. The polyelectrolyte gel according to claim 10, wherein The strain of the polyelectrolyte gel after repair for 5 minutes can reach 20% of the initial strain.

14. A method for preparing the polyelectrolyte gel according to any one of claims 1 to 13, comprising: Mixing and stirring the polyelectrolyte monomer, the solvent, the initiator and the optional cross-linking agent at room temperature to uniformly disperse them to obtain a uniform dispersion; The uniform dispersion is solidified and formed to obtain the polyelectrolyte gel.

15. The method according to claim 14, wherein: The uniform dispersion is cured and formed by ultraviolet light or heating under the conditions of temperature of 25±3° C. and humidity of 30±15%.

16. The method according to claim 15, wherein: The initiator is a photoinitiator, selected from at least one of 2-hydroxy-2-methylpropanedione, 2-oxoglutaric acid, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, trifluoromethanesulfonyl ester, triethylphosphonic acid diphenyloxadiazole and diphenylethylenediamine; or the initiator is a thermal initiator, selected from at least one of ammonium persulfate, potassium persulfate, sodium persulfate and ditoluyl peroxide.

17. The method according to any one of claims 14 to 15, wherein: The crosslinking agent is at least one of polyethylene glycol diacrylate, (octahydro-4,7-methylene-1H-indene-1,5-ylidene)bis(methylene) diacrylate, N,N-methylenebisacrylamide, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, (meth)acrylate ethyleneoxy polyethylene glycol ester and 6,6'-bisamino-3,3'-methylene dibenzoic acid.

18. Application of the polyelectrolyte gel according to any one of claims 1 to 13 and / or the polyelectrolyte gel prepared by the method according to any one of claims 14 to 17 in soft robotics, biomedicine, medical cosmetology, flexible wearable devices and ultra-high resolution printing.

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