WO2024254965A1 - 聚电解质凝胶及其制备方法和应用 - Google Patents

聚电解质凝胶及其制备方法和应用 Download PDF

Info

Publication number
WO2024254965A1
WO2024254965A1 PCT/CN2023/112030 CN2023112030W WO2024254965A1 WO 2024254965 A1 WO2024254965 A1 WO 2024254965A1 CN 2023112030 W CN2023112030 W CN 2023112030W WO 2024254965 A1 WO2024254965 A1 WO 2024254965A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyelectrolyte
solvent
polyelectrolyte gel
salt
trimethylammonium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2023/112030
Other languages
English (en)
French (fr)
Inventor
王朝
陈莉莉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Publication of WO2024254965A1 publication Critical patent/WO2024254965A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/38—Esters containing sulfur
    • 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
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F220/38—Esters containing sulfur
    • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
    • 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
    • C08F220/38—Esters containing sulfur
    • C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/095—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/14—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen

Definitions

  • the present invention belongs to the technical field of functional gels, and in particular relates to a polyelectrolyte gel and a preparation method and application thereof.
  • Gels are formed by the 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 the chemical cross-linking points.
  • the free-link chain model regards the chain segments between the chemical cross-linking points as N links of equal length, and the maximum uniaxial stretch ratio ⁇ max follows ⁇ max ⁇ N 1/2 (J.Mech.Phys.Solids 41,389-412(1993)). Due to the uneven cross-linking of the gel network, the maximum reversible deformation is usually lower than ⁇ max .
  • the elastic strain range of the gel is usually no more than 7 times.
  • the beaded structure was first observed as a chain conformation in a low-concentration hydrophobic polyelectrolyte aqueous solution, as shown in Figure 1. Under the antagonism and balance of long-range electrostatic interactions and short-range hydrophobic interactions, the polyelectrolyte chain undergoes uneven solvation, and polyelectrolytes containing hydrophilic and hydrophobic groups can form a beaded structure, with highly hydrated "strings" connecting "beads" with lower hydration levels.
  • l0 is the length of the "string”
  • Db is the diameter of the "bead”.
  • the mean square rotation radius Rg of the bead follows Rg ⁇ mb1 /3 , mb is the number of monomers in the bead, so the maximum stretch ratio ⁇ max of the bead (the maximum stretch ratio is defined as the ratio between the mean square rotation radius Rg of the fully unfolded polymer chain and the initial bead) follows ⁇ max ⁇ mb2 /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 show a higher degree of contraction and more releasable entropy, thereby achieving a larger elastic deformation. However, there are no reports on the technology of introducing the beaded structure into the gel network structure.
  • the present disclosure aims to solve one of the technical problems in the related art at least to some extent.
  • the present disclosure provides a polyelectrolyte gel and a preparation method and application thereof, and characterizes the structure and performance of the polyelectrolyte gel.
  • the first aspect of the present disclosure provides a polyelectrolyte gel, the raw materials of which include polyelectrolyte monomers and solvents, the polyelectrolyte monomers having 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.
  • the solvent is hydrophilic and is a mixture of any one or more of water, ethylene glycol and glycerol.
  • the solvent-philic ionic group is an ionic group that is easily soluble in water
  • the solvent-phobic and flexible non-ionic group is a polyethylene glycol chain, a carbon chain or a siloxane chain.
  • the structural formula of the polyelectrolyte is any one of -[CH 2 CH(COOR)] n -, [CH 2 C(CH 3 )(COOR)] n -, -[CH 2 CH(CONHR)] n -, -[CH 2 C(CH 3 )(CONHR)] n -, -[CH 2 CHR] n -, -[CH 2 CHR-O] n -, -[CHRCH 2 -O] n -, -[Si(CH 3 )(R)-O-(B) b ] n -, -[SiR 2 -O-(B) b ] n -, -[Si(CH 3 )(OR)-O-(B) b ] n -, and -[Si(OR) 2 -O-(B) b ] n -, wherein n is the degree of polymerization,
  • R is composed of a polycation segment -(M) m -A1 + -(L) l (CH 3 ) k and a free counter ion B1 - , M is -CH 2 - or -CH 2 CH 2 O-, L can be -CH 2 - or -CH 2 CH 2 O-, m, l, k are all repeating unit numbers, 1 ⁇ m ⁇ 5, 0 ⁇ l ⁇ 5, 0 ⁇ k ⁇ 1;
  • A1 + is an organic cation, including quaternary ammonium salt, quaternary phosphonium salt, imidazole and pyridinium cation;
  • B1 - is an anion, including fluorine, chlorine, bromine, iodine, phosphate, sulfonate, carboxylate and sulfate;
  • R is composed of a polyanion segment -(P) p -B2 - -(Q) q (CH 3 ) r and a free counter ion A2 + ,
  • P can be -CH 2 - or -CH 2 CH 2 O-,
  • Q can be -CH 2 - or -CH 2 CH 2 O-,
  • p, q, r are all repeating unit numbers, 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 salt, quaternary phosphonium salt, imidazole and pyridinium cation;
  • B2 - is an anion, including sulfonate, carboxylate, phosphate and sulfate;
  • R is a polyzwitterionic segment -(X) x -A3 + -(Y) y -B3 - -(Z) z (CH 3 ) w or -(X) x -B3 - -(Y) y -A3 + -(Z) z (CH 3 ) w
  • X is -CH 2 - or -CH 2 CH 2 O-
  • Y is -CH 2 - or -CH 2 CH 2 O-
  • Z is -CH 2 - or -CH 2 CH 2 O-
  • x, y, z, w are all the number of repeating units, 1 ⁇ x ⁇ 5, 1 ⁇ y ⁇ 5, 0 ⁇ z ⁇ 5, 0 ⁇ w ⁇ 1
  • A3 + is an organic cation including quaternary ammonium salt, quaternary phosphonium salt, imidazole and pyridinium cation
  • B3 - is an anion including sulfonate,
  • 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 chlor
  • 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.
  • the raw material of the polyelectrolyte gel further comprises an initiator, and the initiator is a photoinitiator selected from 2-hydroxy-2-methylpropanedione, 2-oxoglutaric acid, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1- At least one of acetone, 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 ditoluoyl peroxide.
  • the initiator is a photoinitiator selected from 2-hydroxy-2-methylpropanedione, 2-oxoglutaric acid, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]
  • the raw material of the polyelectrolyte gel further includes a chemical crosslinker, and the chemical crosslinker 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) acrylic acid vinyloxy polyethylene glycol ester and 6,6'-bisamino-3,3'-methylene dibenzoic acid.
  • the content of the chemical crosslinker is 0-0.01 equivalents relative to the polyelectrolyte monomer.
  • the polyelectrolyte chain undergoes uneven solvation, and the molar ratio of the polyelectrolyte monomer to the solvent molecule is between 1:2.5 and 1:12.
  • the molar ratio of the polyelectrolyte monomer to the solvent molecule is between 1:3 and 1:8.
  • 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%.
  • 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 a repairing property.
  • the present disclosure provides a polyelectrolyte having a solvophilic ionic group and a solvophobic and flexible nonionic group, and the conformation of the chain can be conveniently regulated by adjusting the content of the solvent.
  • the solvent molecules are insufficient to completely solvate all polyelectrolyte chains, the solvophobic interaction between the nonionic groups begins to compete with the electrostatic interaction between the ionic groups on the chain, and the flexible polymer chain collapses into a beaded conformation, with highly solvated "strings" connecting "beads” with a lower degree of solvation, thereby minimizing the contact between the nonionic groups and the solvent molecules and maximizing the contact between the ionic groups and the solvent molecules.
  • the high content of polyelectrolyte monomers in the polyelectrolyte gel provided by the present disclosure easily forms tight interchain entanglements to form a physical cross-linked network.
  • the rigid interchain entanglement remains intact to provide physical crosslinking; if the content of the polyelectrolyte chain is not enough to form tight interchain physical entanglements, chemical crosslinking can be provided by adding 0-0.01 equivalents of chemical crosslinking agents relative to the polyelectrolyte monomers.
  • the beaded conformation in the polyelectrolyte gel can be continuously unfolded to increase the polymer chains between the crosslinking points and toughen the polyelectrolyte gel.
  • the chain segments can be reversibly restored to the initial beaded conformation.
  • the reversible stretching process does not involve the breaking of irreversible chemical bonds, and the non-directional electrostatic interaction can completely restore the beaded structure, giving the material mechanical properties that do not decay after repeated tensile tests.
  • a second aspect of the present disclosure provides a method for preparing a polyelectrolyte gel, comprising the following steps:
  • 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.
  • the uniform dispersion is solidified and formed to obtain the polyelectrolyte gel.
  • the uniform dispersion is cured by ultraviolet light or heating at a temperature of 25 ⁇ 3° C. and a humidity of 30 ⁇ 15%.
  • 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.
  • the crosslinking agent is polyethylene glycol diacrylate, (octahydro-4,7-methylene-1H-indene-1,5-ylidene) bis(methylene) diacrylate, N,N-methylenebisacrylamide, polyethylene glycol dimethacrylate, dimethacrylic acid At least one of ethylene glycol ester, ethyleneoxy polyethylene glycol (meth)acrylate and 6,6'-bisamino-3,3'-methylenedibenzoic acid.
  • the preparation method of the polyelectrolyte gel provided by the present disclosure adopts a one-step polymerization method, the preparation process is simple, the raw materials are cheap and easily available, the reaction conditions are mild, the preparation cost is low, and large-scale production is easy.
  • 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.
  • the polyelectrolyte gel provided by the present invention has excellent mechanical strength, elasticity, ionic conductivity, rapid repair performance and biocompatibility, and 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.
  • FIG1 is a schematic diagram of a disclosed beaded structure
  • FIG2 is an AFM height image of a superelastic ion-conducting gel
  • FIG3 is a true stress-strain curve of polyelectrolyte gels with different water contents
  • FIG4 is a true stress-strain curve of cyclic stretching of a superelastic ion conductive gel
  • FIG5 is a cyclic compression stress-strain curve of a superelastic ion conductive gel
  • FIG6 is a rheological test of the storage modulus and loss modulus of the superelastic ion conductive gel as a function of frequency
  • FIG. 7 a is a biaxial elastic display diagram of a pneumatic model made of a superelastic ion conductive gel
  • FIG. 7 b is a finite element simulation diagram of a pneumatic model made of a superelastic ion conductive gel after inflation;
  • FIG8 is a rapid repair performance test of superelastic ion conductive gel
  • FIG9 is a test of the ionic conductivity of the superelastic ion conductive gel before and after rapid repair
  • FIG10 is a pneumatic model made of superelastic ion conductive gel to achieve self-volume sensing
  • FIG. 11 is an impact test of a pneumatic model made of superelastic ion conductive gel.
  • the present disclosure provides a superelastic and rapidly repairable polyelectrolyte gel with ultra-large reversible biaxial surface strain, wherein the polyelectrolyte gel has a beaded structure, comprises a polyelectrolyte and a solvent, wherein the monomer of the polyelectrolyte has a solvent-philic ionic group and a solvent-phobic and flexible non-ionic group, and by adjusting the solvent polarity and solvent content, the polyelectrolyte chain undergoes uneven solvation under the antagonism and balance of long-range electrostatic interaction and short-range solvent-phobic interaction, so that the polyelectrolyte forms a beaded structure, wherein highly solvated "strings" connect "beads" with a lower degree of solvation.
  • the first aspect of the present disclosure provides a polyelectrolyte gel, which uses a polyelectrolyte having a solvent-philic ionic group and a solvent-phobic and flexible non-ionic group.
  • a polyelectrolyte gel which uses a polyelectrolyte having a solvent-philic ionic group and a solvent-phobic and flexible non-ionic group.
  • the conformation of the polyelectrolyte chain can be conveniently controlled.
  • the solvent molecules are insufficient to completely solvate all the polyelectrolyte chains, the solvent-phobic interaction between the non-ionic groups begins to compete with the electrostatic interaction between the ionic groups on the chain, and the flexible polymer chain collapses into a beaded structure.
  • the high content of polyelectrolytes in the gel easily forms tight physical entanglements between chains, which constitute the cross-linking points of the elastic 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 physical entanglements between chains, chemical cross-linking points can be provided by adding 0-0.01 equivalents of chemical cross-linking agents relative to the polyelectrolyte monomers.
  • the polymer chains pulled out of the beads in the beaded structure between the cross-linking points increase the length of the polymer chains between the cross-linking points.
  • the chain segments can quickly and reversibly return to the initial beaded conformation, thus greatly increasing the reversible strain range of the material.
  • the stretching process does not involve irreversible breakage of chemical bonds, and the non-directional electrostatic interaction can completely restore the beaded structure, giving the material mechanical properties that do not decay after repeated stretching tests.
  • the flexible chain segments and a 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.
  • the second aspect of the present disclosure is to provide a method for preparing a polyelectrolyte gel, comprising the following steps:
  • 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%).
  • step (2) pouring the uniform dispersion obtained in step (1) into a mold, and curing by ultraviolet light or heating at a temperature of 25 ⁇ 3° C. and a humidity of 30 ⁇ 15% to obtain a polyelectrolyte gel.
  • the monomers of the polyelectrolyte used in the following examples are: (2-acryloyloxyethyl)trimethylammonium chloride (hereinafter abbreviated as AETC, 80wt% in H2O ), 3-sulfopropyl acrylate potassium salt (hereinafter abbreviated as PSK, 98wt%), acryloyloxyethyl sulfobetaine (hereinafter abbreviated as BA), photoinitiator: 2-hydroxy-2-methylpropanedione (hereinafter abbreviated as HMPP, 98wt%), thermal initiator: benzoyl peroxide (hereinafter abbreviated as BPO, 98wt%) and chemical crosslinker: polyethylene glycol diacrylate (hereinafter abbreviated as PEGDA 400, 98wt%), the solvents are water, ethylene glycol and glycerol; except BA, the other reagents can be purchased from Energy Chemical.
  • Acryloyloxyethyl sulfobetaine (hereinafter referred to as BA) is prepared by the following steps:
  • 0.05 mol 1,3-propane sultone and 10 g acetonitrile were mixed evenly, and then added to a mixture of 0.05 mol dimethylaminoethyl acrylate and 10 g acetonitrile, stirred at 25 °C for 12 h, and then allowed to stand for 36 h.
  • the obtained white precipitate was repeatedly filtered, centrifuged and rinsed with acetonitrile and acetone to obtain powdered acryloyloxyethyl sulfobetaine (BA).
  • the microstructure of the polyelectrolyte gel is characterized by atomic force microscopy (AFM); the mechanical properties, elastic properties and rapid repair properties of the polyelectrolyte gel are characterized by a tensile machine; the rheological properties of the polyelectrolyte gel are characterized by a dynamic rheometer; and the ionic conductivity and sensing properties of the polyelectrolyte gel are characterized by electrochemical impedance spectroscopy (EIS).
  • AFM atomic force microscopy
  • EIS electrochemical impedance spectroscopy
  • Examples 1-13 are used to illustrate the preparation method of polyelectrolyte gel
  • Example 1 Preparation of polyelectrolyte AETC hydrogel (20 wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 3 )] n -nCl - ), the molar ratio of polyelectrolyte monomer to water is 1:2.69, comprising the following steps:
  • step (2) For the sample used for tensile testing, pour the uniform dispersion obtained in step (1) into a dumbbell-shaped polytetrafluoroethylene The sample was placed in an olefin mold and then covered with a transparent square plastic petri dish to minimize water evaporation.
  • the sample was irradiated with ultraviolet light (the ultraviolet light was generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube was 200nm to 420nm, the power was 36W, and the distance between the ultraviolet lamp tube and the sample was 6cm) for 10min to 60min at a temperature of 25 ⁇ 3°C and a humidity of 30 ⁇ 15%, and a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness) was obtained.
  • the ultraviolet light was generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube was 200nm to 420nm, the power was 36W, and the distance between the ultraviolet lamp tube and the sample was 6cm
  • 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.
  • 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
  • Example 2 Preparation of polyelectrolyte AETC hydrogel (25 wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 3 )] n -nCl - ), wherein the molar ratio of polyelectrolyte monomer to water is 1:3.59, comprising the following steps:
  • 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.
  • ultraviolet rays (the ultraviolet rays are 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) are irradiated for 10min to 60min under the conditions of temperature 25 ⁇ 3°C and humidity 30 ⁇ 15%, to obtain a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness).
  • 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.
  • 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
  • Example 3 Preparation of polyelectrolyte AETC hydrogel (30 wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 3 )] n -nCl - ), wherein the molar ratio of polyelectrolyte monomer to water is 1:4.61, comprising the following steps:
  • 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.
  • ultraviolet rays (the ultraviolet rays are 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) are irradiated for 10min to 60min under the conditions of temperature 25 ⁇ 3°C and humidity 30 ⁇ 15%, and a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness) is obtained.
  • 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.
  • 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
  • Example 4 Preparation of polyelectrolyte AETC hydrogel (35 wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 3 )] n -nCl - ), wherein the molar ratio of polyelectrolyte monomer to water is 1:5.8, comprising the following steps:
  • step (2) For the samples used for tensile testing, pour the uniform dispersion obtained in step (1) into a dumbbell-shaped polytetrafluoroethylene mold, and then cover it with a transparent square plastic petri dish to minimize water evaporation.
  • ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm ⁇ 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) are irradiated for 10min ⁇ 60min to obtain a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness).
  • 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.
  • 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
  • Example 5 Preparation of polyelectrolyte AETC hydrogel (30 wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 3 )] n -nCl - ), wherein the molar ratio of polyelectrolyte monomer to water is 1:4.61, comprising the following steps:
  • the uniform dispersion obtained in step (1) is poured into a dumbbell-shaped polytetrafluoroethylene mold, and then covered with a transparent square plastic culture dish to minimize water volatilization.
  • ultraviolet rays (the ultraviolet rays are 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) are irradiated for 10min to 60min under the conditions of temperature 25 ⁇ 3°C and humidity 30 ⁇ 15%, to obtain a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness).
  • 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.
  • 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
  • Example 6 Preparation of chemically cross-linked polyelectrolyte AETC hydrogel (30 wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 3 )] n -nCl - ), wherein the molar ratio of polyelectrolyte monomer to water is 1:4.61, comprising the following steps:
  • step (2) For the sample used for tensile test, pour the uniform dispersion obtained in step (1) into a dumbbell-shaped polytetrafluoroethylene mold, and then cover it with a transparent square plastic petri dish to minimize water volatilization. Subsequently, irradiate 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 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).
  • 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
  • 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.
  • 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
  • Example 7 Preparation of chemically cross-linked polyelectrolyte AETC hydrogel (30 wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 3 )] n -nCl - ), the molar ratio of polyelectrolyte monomer to water is 1:4.61, comprising the following steps:
  • step (2) For the sample used for tensile testing, pour the uniform dispersion obtained in step (1) into a dumbbell-shaped polytetrafluoroethylene The sample was placed in an olefin mold and then covered with a transparent square plastic petri dish to minimize water evaporation.
  • the sample was irradiated with ultraviolet light (the ultraviolet light was generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube was 200nm to 420nm, the power was 36W, and the distance between the ultraviolet lamp tube and the sample was 6cm) for 10min to 60min at a temperature of 25 ⁇ 3°C and a humidity of 30 ⁇ 15%, and a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness) was obtained.
  • the ultraviolet light was generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube was 200nm to 420nm, the power was 36W, and the distance between the ultraviolet lamp tube and the sample was 6cm
  • 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.
  • 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
  • Example 8 Preparation of polyelectrolyte PSK hydrogel (30 wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 3 SO 3 - )] n -nK + ), the molar ratio of polyelectrolyte monomer to water is 1:5.53, comprising the following steps:
  • 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.
  • ultraviolet rays (the ultraviolet rays are 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) are irradiated for 10min to 60min under the conditions of temperature 25 ⁇ 3°C and humidity 30 ⁇ 15%, to obtain a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness).
  • 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.
  • 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
  • Example 9 preparation of chemically cross-linked polyelectrolyte PSK hydrogel (40wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 3 SO 3 - )] n -nK + ), the molar ratio of polyelectrolyte monomer to water is 1:8.6, comprising the following steps:
  • 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.
  • ultraviolet rays (the ultraviolet rays are 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) are irradiated for 10min to 60min under the conditions of temperature 25 ⁇ 3°C and humidity 30 ⁇ 15%, to obtain a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness).
  • 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.
  • 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
  • Example 10 Preparation of polyelectrolyte BA hydrogel (30 wt% H 2 O, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) 3 SO 3 - )] n -nK + ), wherein the molar ratio of polyelectrolyte monomer to water is 1:6.36, comprising the following steps:
  • step (2) For the samples used for tensile testing, pour the uniform dispersion obtained in step (1) into a dumbbell-shaped polytetrafluoroethylene mold, and then cover it with a transparent square plastic petri dish to minimize water evaporation.
  • ultraviolet rays (the ultraviolet rays are generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm ⁇ 420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) are irradiated for 10min ⁇ 60min to obtain a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness).
  • 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.
  • 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
  • Example 11 Preparation of chemically cross-linked polyelectrolyte BA ethylene glycol gel (70 wt% CH 2 OHCH 2 OH, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) 3 SO 3 - )] n -nK + ), the molar ratio of polyelectrolyte monomer to ethylene glycol is 1:10.05, comprising the following steps:
  • step (2) For the sample used for tensile testing, pour the uniform dispersion obtained in step (1) into a dumbbell-shaped polytetrafluoroethylene mold, and then cover it with a transparent square plastic petri dish to minimize volatilization. Then, heat it at a temperature of 60 ⁇ 20°C for 10min-24h to obtain a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness).
  • 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.
  • 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
  • Example 12 Preparation of chemically cross-linked polyelectrolyte BA ethylene glycol gel (70 wt% CH 2 OHCH 2 OH, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) 3 SO 3 - )] n -nK + ), wherein the molar ratio of polyelectrolyte monomer to ethylene glycol is 1:10.05, comprising the following steps:
  • 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.
  • ultraviolet rays (the ultraviolet rays are 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) are irradiated for 10min to 60min under the conditions of temperature 25 ⁇ 3°C and humidity 30 ⁇ 15%, to obtain a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness).
  • 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.
  • 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
  • Example 13 Preparation of chemically cross-linked polyelectrolyte BA glycerol gel (80 wt% CH 2 OHCHOHCH 2 OH, -[CH 2 CH(COO(CH 2 ) 2 N + (CH 3 ) 2 (CH 2 ) 3 SO 3 - )] n -nK + ), the molar ratio of polyelectrolyte monomer to glycerol is 1:11.6, comprising the following steps:
  • step (2) For the samples used for tensile testing, pour the uniform dispersion obtained in step (1) into a dumbbell-shaped polytetrafluoroethylene mold, and then cover it with a transparent square plastic petri dish to minimize evaporation.
  • ultraviolet light (the ultraviolet light is generated by an ultraviolet lamp, the wavelength of the ultraviolet lamp tube is 200nm-420nm, the power is 36W, and the ultraviolet lamp tube is 6cm away from the sample) is irradiated for 10min-60min to obtain a barbell-shaped tensile specimen with a main body size of 20mm ⁇ 10mm ⁇ 2.5 ⁇ 0.1mm (length ⁇ width ⁇ thickness).
  • 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.
  • 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
  • Example 2 Cut 2 mg of the sample in Example 2 (containing 25 wt % water) and immerse it in 1 ml of deionized water and stir it thoroughly.
  • the bright spheres indicated by the letter A correspond to the beads in the beaded structure
  • 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, which corresponds to the polymer chain partially collapsing into a spherical conformation under the balance of electrostatic and hydrophobic effects, and the spherical conformations are connected by linear polymer chains.
  • a uniaxial tensile test was performed on a barbell-shaped tensile specimen having 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%.
  • the two ends of the sample are bonded with a thick material and clamped with a tensile testing machine to reduce slippage.
  • the initial length between the clamps is 10 ⁇ 1 mm.
  • true stress nominal stress ⁇ (strain/100+1), the unit of strain is %, and the tensile strain of 1 times is 100%, so the use of the true stress can better reflect the tensile condition of the material.
  • the obtained polyelectrolyte gel has good 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 about 11.5MPa.
  • the cyclic stress-strain tensile curves with a four-fold uniaxial strain of 1500% can basically completely overlap.
  • the material exhibits a fully reversible uniaxial elastic deformation of up to 15 times, see Figure 4.
  • a compressive stress-strain test was performed on a 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%.
  • 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 the first cycle, see FIG5 .
  • the applied axial force is 1 N
  • the angular frequency sweep range is 0.1 to 100 rad s -1
  • the shear strain is constant at 1%.
  • the external contour of the pneumatic model was 23 mm in length ⁇ 17 mm in width ⁇ 6 mm in height, and the internal cavity was 15 mm in length ⁇ 9 mm in width ⁇ 4 mm in height.
  • Example 2 the polyelectrolyte gel prepared in Example 2 was used to perform electrochemical impedance spectroscopy (EIS), as shown in FIG8 .
  • EIS electrochemical impedance spectroscopy
  • the polyelectrolyte gel After 1 second of repair, the polyelectrolyte gel has the same electrochemical impedance properties as that of the undamaged polyelectrolyte gel, and its ionic conductivity is about 4.9 mS/cm.
  • step (1) of Example 2 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.
  • Example 2 The barbell-shaped tensile specimen in Example 2 was cut into two halves using a fresh blade and pressed by hand for different time periods at ambient temperature (24 ⁇ 1° C.).
  • 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, wherein the outer contour thereof was 23 mm in length ⁇ 17 mm in width ⁇ 6 mm in height, and the inner cavity thereof was 15 mm in length ⁇ 9 mm in width ⁇ 4 mm in height.
  • 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, wherein the outer contour thereof was 23 mm in length ⁇ 17 mm in width ⁇ 6 mm in height, and the inner cavity thereof was 15 mm in length ⁇ 9 mm in width ⁇ 4 mm in height.
  • a sample of a specific shape is prepared using the uniform dispersion obtained in step (1) of Example 2, and then a cubic pneumatic model is obtained by photocuring and splicing, wherein the outer contour thereof is 40 mm in length ⁇ 40 mm in width ⁇ 40 mm in height, and the inner cavity thereof is 30 mm in length ⁇ 30 mm in width ⁇ 30 mm in height.
  • the preparation method of the polyelectrolyte gel provided in 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 performance, and can quickly repair various small mechanical injuries, 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.
  • the polyelectrolyte gel of the embodiment of the present disclosure and its design concept are very useful in soft robots, superelastic electrodes, drug delivery carriers, tissue engineering scaffolds, bioelectronics, wound dressings, contact lenses, electrodes It has broad application prospects in batteries and supercapacitors, optical devices, acoustic devices, energy converters, bioadhesives, coatings, medical cosmetology, ultra-high resolution printing and other fields.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

本公开提供了一种聚电解质凝胶及其制备方法和应用，原料包括聚电解质单体和溶剂，所述聚电解质的单体具有亲溶剂的离子基团与疏溶剂且柔性的非离子基团，通过调节溶剂极性与溶剂含量，在远程静电相互作用和短程疏溶剂相互作用的拮抗与平衡下，聚电解质链发生不均匀溶剂化，使所述聚电解质形成串珠结构。所述聚电解质凝胶的制备方法包括将均匀分散的混合原料固化成型得到所述聚电解质凝胶。可将所述聚电解质凝胶应用于软体机器人、生物医药、医疗美容、柔性可穿戴设备和超高分辨率打印中。

Description

聚电解质凝胶及其制备方法和应用
相关申请的交叉引用
本申请基于申请号为202310715758.2、申请日为2023年06月16日的中国专利申请提出，并要求该中国专利申请的优先权，该中国专利申请的全部内容在此引入本申请作为参考。
技术领域
本公开属于功能性凝胶技术领域，具体地涉及一种聚电解质凝胶及其制备方法和应用。
背景技术
凝胶是由交联聚合物网络在溶剂分子中溶胀形成的。凝胶的弹性一般来自于化学交联点之间可逆的聚合物链构象变化。自由连接链模型将化学交联点之间的链段看作是长度相等的N个链接，最大单轴拉伸比λmax遵循λmax～N1/2(J.Mech.Phys.Solids 41,389-412(1993))，由于凝胶网络的不均匀交联，最大可逆变形通常要低于λmax。通常地，受限于凝胶网络中交联点之间的链段数目N，凝胶的弹性应变范围通常不超过7倍。最近，Ito等人开发了一种非固定交联的滑环交联策略，利用链上可滑动的轮烷，拉取原本横向取向的链段得到更多的纵向拉伸增益，从而将单轴弹性变形极限提高到了1,000％范围(Science 372,1078-1081(2021))。然而，双轴弹性变形面临着更大的挑战，因为链段沿着两个方向延伸，共价交联严重限制了双轴拉伸下的变形能力。等双轴拉伸断裂下最大的线应变至少比单轴拉伸下低30％(Trans.Soc.Rheol.15,91-110(1971))，更不要提可逆的双轴面应变。迄今为止，具有大于2,500％的可逆双轴面应变的弹性凝胶仍未报道。
串珠结构最早是在低浓度疏水聚电解质水溶液中观察到的链构象，如图1所示。在远程静电相互作用和短程疏水相互作用的拮抗与平衡下，聚电解质链发生不均匀溶剂化，含有亲水和疏水基团的聚电解质可以形成串珠结构，高度水合的“弦”连接着水合程度较低的“珠子”，图1中，l0是“弦”的长度，Db是“珠子”的直径。珠子的均方旋转半径Rg遵循Rg～mb 1/3，mb为珠子内单体数，因此珠子的最大拉伸比λmax(将该最大拉伸比定义为完全展开的聚合物链和初始珠子的均方旋转半径Rg之间的比率)遵循λmax～mb 2/3(Prog.Polym.Sci 30,1049-1118(2005))。因此，在与相同N值下自由连接链模型相比，可逆的串珠链构象能表现出更高程度的收缩和更多可释放的熵，从而可以实现更大的弹性变形。然而，目前还未见将串珠结构引入凝胶网络结构的相关技术报道。
发明内容
本公开旨在至少在一定程度上解决相关技术中的技术问题之一。
为了克服上面所述的技术问题，本公开提供了一种聚电解质凝胶及其制备方法和应用，并对所述聚电解质凝胶的结构与性能进行了表征。
本公开第一方面提供了一种聚电解质凝胶，所述聚电解质凝胶的原料包含聚电解质单体和溶剂，所述聚电解质单体具有亲溶剂的离子基团与疏溶剂且柔性的非离子基团，通过调节溶剂极性与溶剂含量，在远程静电相互作用和短程疏溶剂相互作用的拮抗与平衡下，聚电解质链发生不均匀溶剂化，使所述聚电解质形成串珠结构。
在一些实施例中，所述溶剂具有亲水性，选用水、乙二醇和丙三醇中的任意一种或多种的混合物。
在一些实施例中，所述聚电解质的单体中，所述亲溶剂的离子基团为易溶于水的离子基团，所述疏溶剂且柔性的非离子基团为聚乙二醇链、碳链或硅氧烷链。
在一些实施例中，所述聚电解质的结构式为-[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-和-[Si(OR)2-O-(B)b]n-中的任意一种，n为聚合度，n≧2，(B)b为-[CH2CH2O]b-，b≥0，R为以下任意一种或多种含离子的有机侧链且要求所选的多种含离子的有机侧链之间不发生聚沉：
R由聚阳离子链段-(M)m-A1+-(L)l(CH3)k和游离对离子B1-构成，M为-CH2-或-CH2CH2O-，L可为-CH2-或-CH2CH2O-，m、l、k均为重复单元数，1≤m≤5，0≤l≤5,0≤k≤1；A1+为有机阳离子，包括季铵盐、季鏻盐、咪唑和吡啶鎓阳离子；B1-为阴离子，包括氟、氯、溴、碘、磷酸根、磺酸根、羧酸根和硫酸根；
R由聚阴离子链段-(P)p-B2--(Q)q(CH3)r和游离对离子为A2+构成，P可为-CH2-或-CH2CH2O-，Q可为-CH2-或-CH2CH2O-，p、q、r均为重复单元数，1≤p≤5，0≤q≤5,0≤r≤1；A2+为金属或有机阳离子，包括锂、钠、钾、镁、钙、钡、锌、银、铁、铝、铜、季铵盐、季鏻盐、咪唑和吡啶鎓阳离子；B2-为阴离子，包括磺酸根、羧酸根、磷酸根和硫酸根；
R为聚两性离子链段-(X)x-A3+-(Y)y-B3--(Z)z(CH3)w或-(X)x-B3--(Y)y-A3+-(Z)z(CH3)w，X为-CH2-或-CH2CH2O-，Y为-CH2-或-CH2CH2O-，Z为-CH2-或-CH2CH2O-，x、y、z、w均为重复单元数，1≤x≤5，1≤y≤5，0≤z≤5，0≤w≤1；A3+为有机阳离子，包括季铵盐、季鏻盐、咪唑和吡啶鎓阳离子；B3-为阴离子，包括磺酸根、羧酸根、磷酸根和硫酸根。
在一些实施例中，所述聚电解质选用以下任意一种或多种彼此之间不会发生聚沉的电解质单体：(2-丙烯酰氧基乙基)三甲基氯化铵、(2-丙烯酰氧基乙基)三甲基溴化铵、(2-丙烯酰氧基乙基)三甲基碘化铵、(3-丙烯酰氧基丙基)三甲基氯化铵、(3-丙烯酰氧基丙基)三甲基溴化铵、(3-丙烯酰氧基丙基)三甲基碘化铵、(2-丙烯酰氧基丁基)三甲基氯化铵、(2-丙烯酰氧基丁基)三甲基溴化铵、(2-丙烯酰氧基丁基)三甲基碘化铵、(3-丙烯酰胺丙基)三甲基氯化铵、(3-丙烯酰胺丙基)三甲基溴化铵、(3-丙烯酰胺丙基)三甲基碘化铵、(2-丙烯酰胺丁基)三甲基氯化铵、(2-丙烯酰胺丁基)三甲基溴化铵、(2-丙烯酰胺丁基)三甲基碘化铵、(5-丙烯酰氨基戊基)三甲基氯化铵、(5-丙烯酰氨基戊基)三甲基溴化铵、(5-丙烯酰氨基戊基)三甲基碘化铵、丙烯酸3-磺丙酯钾盐、丙烯酸3-磺丙酯钠盐、丙烯酸3-磺丙酯锂盐、丙烯酸2-磺乙酯钠盐、丙烯酸2-磺乙酯钾盐、丙烯酸2-磺乙酯锂盐、丙烯酸4-磺丁酯钾盐、丙烯酸4-磺丁酯钠盐、丙烯酸4-磺丁酯锂盐、丙烯酰胺2-磺乙酯钠盐、丙烯酰胺2-磺乙酯钾盐、丙烯酰胺2-磺乙酯锂盐、丙烯酰胺3-磺丙酯钾盐、丙烯酰胺3-磺丙酯钠盐、丙烯酰胺3-磺丙酯锂盐、丙烯酰胺4-磺丁酯钾盐、丙烯酰胺4-磺丁酯钠盐、丙烯酰胺4-磺丁酯锂盐、丙烯酰氧乙基磺基甜菜碱、丙烯酰氧乙基二甲基铵丙酸酯、丙烯酰胺丙基二甲基铵乙酸酯和丙烯酰氧乙基磷酸胆碱。
在一些实施例中，聚电解质凝胶通过含有乙烯双键的电解质单体或硅氧烷电解质或聚乙二醇电解质、溶剂、引发剂的均匀混合溶液在紫外光照或加热下发生自由基聚合制备。
在一些实施例中，所述聚电解质凝胶的原料还包括引发剂，所述引发剂为光引发剂，选自2-羟基-2-甲基丙二酮、2-氧代戊二酸、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1- 丙酮、2,4,6(三甲基苯甲酰基)二苯基氧化膦、三氟甲磺酰酯、三乙磷酸二苯基二唑和二苯基乙烯二胺中的至少一种；或者所述引发剂为热引发剂，选自过硫酸铵、过硫酸钾、过硫酸钠和过氧化二甲苯酰中的至少一种。
在一些实施例中，所述聚电解质凝胶的原料还包括化学交联剂，所述化学交联剂选用聚乙二醇二丙烯酸酯、(八氢-4,7-亚甲基-1H-茚-1,5-亚基)双(亚甲基)二丙烯酸酯、N,N-亚甲基双丙烯酰胺、聚乙二醇二甲基丙烯酸酯、二甲基丙烯酸乙二醇酯、(甲基)丙烯酸乙烯氧基聚乙二醇酯和6,6'-双氨基-3,3'-甲叉基二苯甲酸中的至少一种。在一些实施例中，所述化学交联剂的含量为相对于所述聚电解质单体0-0.01个当量。在一些实施例中，在形成所述凝胶之前的溶液体系中，聚电解质链发生不均匀溶剂化，聚电解质单体与所述溶剂分子的摩尔比在1:2.5～1:12之间。
在一些实施例中，所述聚电解质单体与所述溶剂分子的摩尔比在1:3-1:8之间。
在一些实施例中，所述聚电解质凝胶具有各向同性，且具有700％～1500％的可逆单轴应变和3000％～10,000％的可逆双轴面应变。
在一些实施例中，所述聚电解质凝胶经5min修复后的应变达到初始应变的20％。由此，本申请提供的聚电解质凝胶具有修复性质。
本公开提供了一种具有亲溶剂的离子基团和疏溶剂且柔性的非离子基团的聚电解质，通过调节溶剂的含量，可以方便地调控链的构象。当溶剂分子不足以完全溶剂化所有聚电解质链时，非离子基团之间的疏溶剂作用开始能与链上的离子基团之间的静电作用竞争，柔性的聚合物链将塌缩成串珠构象，高度溶剂化的“弦”连接着溶剂化程度较低的“珠子”，从而最小化非离子基团与溶剂分子的接触，并最大化离子基团与溶剂分子的接触。
本公开提供的聚电解质凝胶中高含量的聚电解质单体容易形成紧密的链间缠结，构成物理交联网络。在一定范围内无论施加大的单轴或双轴应变，刚性链间纠缠仍然保持完整以提供物理交联；若聚电解质链的含量不足以形成紧密的链间物理缠结，可额外通过加入相对于聚电解质单体0-0.01个当量的化学交联剂来提供化学交联。在材料被施加足够的应变时，聚电解质凝胶中的串珠构象可以被连续展开从而增长交联点之间的聚合物链，并增韧聚电解质凝胶，在卸去应力后，链段可以可逆地恢复到初始的串珠构象。此外，可逆拉伸过程不涉及不可逆的化学键的断裂，且无方向性的静电相互作用可以使串珠结构完全恢复，赋予材料在重复拉伸测试后不衰减的机械性质。
本公开第二方面提供一种聚电解质凝胶的制备方法，包括以下步骤：
将聚电解质单体、溶剂、引发剂以及可选的交联剂，在室温下混合搅拌，使其均匀分散以获得均匀分散液。
将所述均匀分散液固化成型，得到所述聚电解质凝胶。
在一些实施例中，所述均匀分散液在温度25±3℃、湿度30±15％的条件下通过紫外光照或加热固化成型。
在一些实施例中，所述引发剂为光引发剂，选自2-羟基-2-甲基丙二酮、2-氧代戊二酸、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、2,4,6(三甲基苯甲酰基)二苯基氧化膦、三氟甲磺酰酯、三乙磷酸二苯基二唑和二苯基乙烯二胺中的至少一种；或者引发剂为热引发剂，选自过硫酸铵、过硫酸钾、过硫酸钠和过氧化二甲苯酰中的至少一种。
在一些实施例中，所述交联剂为聚乙二醇二丙烯酸酯、(八氢-4,7-亚甲基-1H-茚-1,5-亚基)双(亚甲基)二丙烯酸酯、N,N-亚甲基双丙烯酰胺、聚乙二醇二甲基丙烯酸酯、二甲基丙烯酸 乙二醇酯、(甲基)丙烯酸乙烯氧基聚乙二醇酯和6,6'-双氨基-3,3'-甲叉基二苯甲酸中的至少一种。
本公开提供的聚电解质凝胶的制备方法采用一步聚合的方法，制备过程简单，原料廉价易得，反应条件温和，制备成本低，容易规模化生产。
本公开第三方面提供一种聚电解质凝胶在软体机器人、生物医药、医疗美容、柔性可穿戴设备和超高分辨率打印中的应用。
本公开提供的聚电解质凝胶具有优异的机械强度、弹性性能、离子导电性、快速修复性能与生物相容性，可将上述聚电解质凝胶应用于软体机器人、生物医药、医疗美容、柔性可穿戴设备和超高分辨率打印的相关领域。
附图说明
图1是已公开的串珠结构的示意图；
图2是超弹性离子导电凝胶的AFM高度图；
图3是不同水含量的聚电解质凝胶的真实应力-应变曲线；
图4是超弹性离子导电凝胶的循环拉伸真实应力-应变曲线；
图5是超弹性离子导电凝胶的循环压缩应力-应变曲线；
图6是超弹性离子导电凝胶的储能模量与损耗模量随频率变化的流变测试；
图7a是由超弹性离子导电凝胶制成的气动模型的双轴弹性展示图，图7b是由超弹性离子导电凝胶制成的气动模型的充气后的有限元模拟图；
图8是超弹性离子导电凝胶的快速修复性能测试；
图9是超弹性离子导电凝胶快速修复前后的离子导电性能测试；
图10是超弹性离子导电凝胶制成的气动模型实现自体体积传感；
图11是超弹性离子导电凝胶制成的气动模型的抗冲击测试。
具体实施方式
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合实施例，对本申请进行进一步详细描述。应当理解，此处所描述的具体实施例仅仅用于解释本申请，并不用于限定本申请。相反，本申请涵盖任何由权利要求定义的在本申请精髓和范围上做的替代、修改、等效方法以及方案。进一步，为了使公众对本申请有更好的了解，在下文对本申请的细节描述中，详尽描述了一些特定的细节部分。对本领域技术人员来说没有这些细节部分的描述也可以完全理解本申请。
本公开提供了一种具有超大可逆双轴面应变的超弹性且可快修复的聚电解质凝胶，所述聚电解质凝胶具有串珠结构，包含聚电解质和溶剂，所述聚电解质的单体具有亲溶剂的离子基团与疏溶剂且柔性的非离子基团，通过调节溶剂极性与溶剂含量，在远程静电相互作用和短程疏溶剂相互作用的拮抗与平衡下，聚电解质链发生不均匀溶剂化，使所述聚电解质形成串珠结构，高度溶剂化的“弦”连接着溶剂化程度较低的“珠子”。
本公开第一方面提供的一种聚电解质凝胶，选用具有亲溶剂的离子基团和疏溶剂且柔性的非离子基团的聚电解质，通过调节溶剂的含量，可以方便地调控聚电解质链的构象。当溶剂分子不足以完全溶剂化所有聚电解质链时，非离子基团之间的疏溶剂作用开始能与链上的离子基团之间的静电作用竞争，柔性的聚合物链将塌缩成串珠结构，高度溶剂化(是指在溶 液中，溶质全部被溶剂分子包围，没有游离于分子环绕之外的离子)的“弦”连接着溶剂化程度较低的“珠子”，从而最小化非离子基团与溶剂分子的接触，并最大化离子基团与溶剂分子的接触。
凝胶中高含量的聚电解质容易形成紧密的链间物理缠结，构成弹性网络的交联点，在一定范围内无论施加大的单轴或双轴应变，刚性链间纠缠仍然保持完整以提供物理交联。若聚电解质链的含量不足以形成紧密的链间物理缠结，可额外通过加入相对于聚电解质单体0-0.01个当量的化学交联剂来提供化学交联点，在材料被施加足够的应变时，交联点之间的串珠结构中除了链上被拉直的弦，从珠子中拉出来的聚合物链增长了交联点之间的聚合物链长度，并且得益于串珠结构的低能态和熵驱动，在卸去应力后，链段可以快速可逆地回复到初始的串珠构象，因此可以极大增加材料的可逆应变范围。同时，拉伸过程不涉及化学键的不可逆断裂，而无方向性的静电相互作用可以使串珠结构完全恢复，赋予材料在重复拉伸测试后不衰减的机械性质。此外，柔性的链段与大量的静电相互作用赋予凝胶快速修复的性质，材料本征的离子特性为自传感奠定了基础。
本公开第二方面是提供的一种聚电解质凝胶的制备方法，包括以下步骤：
(1)将一定摩尔量的聚电解质单体，与相当于聚电解质单体2.5-12个当量的溶剂，相当于聚电解质单体0.00002-0.01个当量的引发剂，相当于聚电解质单体0-0.01个当量的化学交联剂，在室温下混合搅拌，得到均匀分散液(该均匀分散液中，聚电解质的单体的摩尔分数在7.7％～28.6％，溶剂分子的摩尔分数在71.4％～92.3％)。
(2)将步骤(1)得到的均匀分散液倒入模具中，在温度25±3℃、湿度30±15％条件下通过紫外光照或加热固化成型，得到聚电解质凝胶。
以下实施例采用的聚电解质的单体为：(2-丙烯酰氧基乙基)三甲基氯化铵(以下简写为AETC,80wt％in H2O)，丙烯酸3-磺丙酯钾盐(以下简写为PSK，98wt％)，丙烯酰氧乙基磺基甜菜碱(以下简写为BA)，光引发剂：2-羟基-2-甲基丙二酮(以下简写为HMPP，98wt％)，热引发剂：过氧化苯甲酰(以下简写为BPO，98wt％)和化学交联剂：聚乙二醇二丙烯酸酯(以下简写为PEGDA 400，98wt％)，溶剂为水、乙二醇、丙三醇；除BA外，其余试剂均可从Energy Chemical购买。
丙烯酰氧乙基磺基甜菜碱(以下简写为BA)是通过以下步骤制得的：
将0.05mol 1,3-丙烷磺酸内酯和10g乙腈混合均匀后，添加到0.05mol丙烯酸二甲氨基乙酯和10g乙腈的混合物中，在25℃下搅拌12h，然后静置36h，得到的白色沉淀物用乙腈、丙酮反复抽滤、离心、冲洗后得到粉末状的丙烯酰氧乙基磺基甜菜碱(BA)。
在本申请中，利用原子力显微镜(AFM)表征聚电解质凝胶的微观结构；利用拉力机表征聚电解质凝胶的机械性能，弹性性能与快速修复性能；利用动态流变仪表征聚电解质凝胶的流变学性质；通过电化学阻抗法(EIS)表征聚电解质凝胶的离子导电与传感性质。这些性能测试过程将在下文给出的各个实施例中详细阐述。
实施例1-13用于说明聚电解质凝胶的制备方法
实施例1、聚电解质AETC水凝胶(20wt％H2O,-[CH2CH(COO(CH2)2N+(CH3)3)]n-nCl-)制备，聚电解质单体与水的摩尔比为1:2.69，包括以下步骤：
(1)将20mmol AETC(包含53.8mmol水)和0.0013mmol光引发剂HMPP混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙 烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例2、聚电解质AETC水凝胶(25wt％H2O,-[CH2CH(COO(CH2)2N+(CH3)3)]n-nCl-)的制备，聚电解质单体与水的摩尔比为1:3.59，包括以下步骤：
(1)将20mmol AETC(包含53.8mmol水)、再加入18mmol去离子水和0.0013mmol光引发剂HMPP混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例3、聚电解质AETC水凝胶(30wt％H2O,-[CH2CH(COO(CH2)2N+(CH3)3)]n-nCl-)的制备，聚电解质单体与水的摩尔比为1:4.61，包括以下步骤：
(1)将20mmol AETC(包含53.8mmol水)、再加入38.4mmol去离子水和0.0013mmol光引发剂HMPP混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)中得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30±15％条件下紫外线紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例4、聚电解质AETC水凝胶(35wt％H2O,-[CH2CH(COO(CH2)2N+(CH3)3)]n-nCl-)的制备，聚电解质单体与水的摩尔比为1:5.8，包括以下步骤：
(1)将20mmol AETC(包含53.8mmol水)、再加入62.1mmol去离子水、0.0013mmol光引发剂HMPP混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30 ±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例5、聚电解质AETC水凝胶(30wt％H2O,-[CH2CH(COO(CH2)2N+(CH3)3)]n-nCl-)的制备，聚电解质单体与水的摩尔比为1:4.61，包括以下步骤：
(1)将20mmol AETC(包含53.8mmol水)、再加入18mmol去离子水、0.0066mmol光引发剂HMPP混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)中的溶液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例6、化学交联聚电解质AETC水凝胶(30wt％H2O,-[CH2CH(COO(CH2)2N+(CH3)3)]n-nCl-)的制备，聚电解质单体与水的摩尔比为1:4.61，包括以下步骤：
(1)将20mmol AETC(包含53.8mmol水)、再加入62.1mmol去离子水、0.0013mmol光引发剂HMPP、0.00013mmol交联剂PEGDA400混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min,获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例7、化学交联聚电解质AETC水凝胶(30wt％H2O,-[CH2CH(COO(CH2)2N+(CH3)3)]n-nCl-)的制备，聚电解质单体与水的摩尔比为1:4.61，包括以下步骤：
(1)将20mmol AETC(包含53.8mmol水)、62.1mmol去离子水、0.0018mmol光引发剂HMPP、0.0056mmol交联剂PEGDA400混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙 烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例8、聚电解质PSK水凝胶(30wt％H2O,-[CH2CH(COO(CH2)3SO3 -)]n-nK+)的制备，聚电解质单体与水的摩尔比为1:5.53，包括以下步骤：
(1)将20mmol PSK、110.6mmol去离子水和0.0018mmol光引发剂HMPP混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例9、化学交联聚电解质PSK水凝胶(40wt％H2O,-[CH2CH(COO(CH2)3SO3 -)]n-nK+)的制备，聚电解质单体与水的摩尔比为1:8.6，包括以下步骤：
(1)将20mmol PSK、172.1mmol去离子水、0.0018mmol光引发剂HMPP和0.0013mmol交联剂PEGDA400混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例10、聚电解质BA水凝胶(30wt％H2O,-[CH2CH(COO(CH2)2N+(CH3)2(CH2)3SO3 -)]n-nK+)的制备，聚电解质单体与水的摩尔比为1:6.36，包括以下步骤：
(1)将20mmol BA、127.3mmol去离子水，0.002mmol光引发剂HMPP和0.002mmol交联剂PEGDA400混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少水分挥发。随后，在温度25±3℃、湿度30 ±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例11、化学交联聚电解质BA乙二醇凝胶(70wt％CH2OHCH2OH,-[CH2CH(COO(CH2)2N+(CH3)2(CH2)3SO3 -)]n-nK+)的制备，聚电解质单体与乙二醇的摩尔比为1:10.05，包括以下步骤：
(1)将20mmol BA、201mmol乙二醇，0.003mmol热引发剂BPO和0.002mmol交联剂PEGDA400混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少挥发。随后，在温度60±20℃下加热10min-24h，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例12、化学交联聚电解质BA乙二醇凝胶(70wt％CH2OHCH2OH,-[CH2CH(COO(CH2)2N+(CH3)2(CH2)3SO3 -)]n-nK+)的制备，聚电解质单体与乙二醇的摩尔比为1:10.05，包括以下步骤：
(1)将20mmol BA、201mmol乙二醇，0.003mmol光引发剂HMPP，0.001mmol交联剂PEGDA400混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少挥发。随后，在温度25±3℃、湿度30±15％条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
实施例13、化学交联聚电解质BA丙三醇凝胶(80wt％CH2OHCHOHCH2OH,-[CH2CH(COO(CH2)2N+(CH3)2(CH2)3SO3 -)]n-nK+)的制备，聚电解质单体与丙三醇的摩尔比为1:11.6，包括以下步骤：
(1)将20mmol BA、232mmol丙三醇和0.003mmol光引发剂HMPP和0.002mmol交联剂PEGDA400混合搅拌3小时，得到均匀分散液。
(2)对于用于拉伸测试的样品，将步骤(1)得到的均匀分散液倒入哑铃状的聚四氟乙烯模具中，再覆盖透明方形塑料培养皿尽量减少挥发。随后，在温度25±3℃、湿度30±15％ 条件下紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射10min～60min，获得主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样。
或者，对于用于压缩测试的样品，将步骤(1)得到的均匀分散液倒入圆筒模具中，紫外线(由紫外灯产生该紫外线，紫外灯的灯管波长为200nm～420nm，功率为36W，紫外灯灯管距离样品6cm)照射20min，得到直径10mm、高度10mm的圆柱形压缩试样。
以下对本公开实施例的有效性进行验证：
1.聚电解质凝胶的结构表征
分析例1
(1)用双面胶布将云母片粘在铁片上，然后用磨砂胶布将云母片剥离，得到干净而平整的表面。
(2)将实施例2中的样品(含25wt％水分)切割2mg浸入1ml去离子水中，充分搅拌。
(3)接下来，用移液管取出10μL(2)中的聚电解质水溶液(1.5mg/mL)，滴到云母片上。
(4)等待10分钟至水分蒸发到肉眼看不到明显的水分时，拍摄AFM高度图像，如图2所示。在AFM高度图像中，如字母A所指示的亮色的球形对应着串珠结构中的珠子，字母B所指示的窄而细的亮线对应着串珠结构中的弦。串珠结构就是由弦将珠子连接起来，对应着高分子链在静电作用与疏水作用的平衡下局部塌缩成球状构象，球状构象之间由线性的高分子链连接起来。
2.聚电解质凝胶的机械性能表征
分析例2
(1)在温度为25±3℃，湿度为30±15％的条件下对实施例2中主体尺寸为20mm×10mm×2.5±0.1mm(长×宽×厚)的杠铃状拉伸试样进行单轴拉伸测试。
(2)样品两端再用一片厚的材料粘接，用拉力机夹紧以减少滑移，夹具之间的初始长度为10±1mm。
(3)除非另有说明，所有拉伸试验均以100mm min-1的加载速率进行。循环拉伸测试的两次加载之间松开夹具，让试样受力为零，松弛时间为1min。每条曲线至少重复三个独立样品。
(4)不同制备条件下的聚电解质凝胶的拉伸曲线如图3所示(水在聚电解质凝胶中的质量分数分别为20wt％、25wt％、30wt％、35wt％)，分别对应实施例1，实施例2，实施例3，实施例4中的样品。需要说明的是，名义应力等于力除以材料初始的横截面积，由于本公开实施例的材料拉伸性较高，横截面积变化极大，势必与加载过程产生的名义应力产生一定的数据偏差；而真实应力假定材料体积守恒，将横截面积的变化考虑进来，满足以下关系：真实应力＝名义应力×(应变/100+1)，应变单位为％，拉伸1倍应变则为100％，因此采用真实应力能更好地反映材料的拉伸情况。
(5)在水的质量分数为25wt％的情况下，所得到的聚电解质凝胶同时具有较好的拉伸性能，力学强度与弹性性能。在断裂前可以单轴拉伸到原长的3000％，可承受最大单轴真实应力约为11.5MPa，四次单轴应变为1500％的循环应力-应变拉伸曲线可以基本完全重合， 展现了材料高达15倍的完全可逆的单轴弹性形变，参见图4。
分析例3
(1)在温度为25±3℃，湿度为30±15％的条件下对实施例2中直径为10mm、高度为10mm的圆柱体试样进行压缩应力-应变测试。
(2)除另有说明外，循环压缩应力-应变曲线均以加载速率为500mm min-1进行，两次循环之间的松弛时间为1s。每条曲线至少重复三个独立样品。
(3)所得到的聚电解质凝胶具有优异的压缩弹性性能，1000圈压缩应变为60％的压缩应力-应变曲线与第一圈基本重合，参见图5。
分析例4
(1)用动态流变仪测定实施例2中聚电解质凝胶的储存模量(G’)和损耗模量(G”)。
(2)制备厚度为1.2mm，直径为20mm的聚电解质凝胶圆片。
(3)施加的轴向力为1N，角频率扫频范围为0.1～100rad s-1，剪切应变恒定为1％。
(4)从附图6的结果可以看出，储能模量远大于损耗模量，说明聚电解质凝胶在0.1～100rad s-1角频率范围内均处于橡胶平台。
分析例5
(1)用实施例2中步骤(1)中得到的均匀分散液制备成特定形状的样品，再通过光固化拼接得到一个具有V0＝0.54mL的内部空腔的长方体的气动模型，其外部轮廓为长×宽×高为23mm×17mm×6mm，其内部空腔为长×宽×高为15mm×9mm×4mm。
(2)使用针筒在气动模型中的空腔内充入550mL空气(内部空腔体积变化约1000倍)，再用针筒将空气抽出，材料形状可以完全恢复(图7a所示)。
(3)通过Abaqus有限元模拟分析例5步骤(2)中的过程，如图7b所示，可逆的最大线应变达到了1377％，展现了大于10,000％的可恢复的双轴弹性面应变。
3.聚电解质凝胶的离子导电与传感性能表征
分析例6
(1)在本实施例中，采用实施例2制备的聚电解质凝胶进行电化学阻抗测试(EIS)，如图8所示。
(2)修复1s后与未损伤时的聚电解质凝胶具有相同的电化学阻抗性质，其离子电导率约为4.9mS/cm。
分析例7
(1)用实施例2中步骤(1)中得到的均匀分散液制备成特定形状的样品，再通过光固化拼接得到一个抓手模型。
(2)对抓手模型通入不同体积的气体，测量R-t曲线，计算电阻随通入气体体积的变化，参见图9，电阻随体积变化明显，本实施例的聚电解质凝胶可以作为优异的传感材料。
4.聚电解质凝胶的快修复性能表征
分析例8
(1)使用新鲜刀片将实施例2中的杠铃状拉伸试样切成两半，在环境温度(24±1℃)下用手按压不同时间。
(2)将(1)中修复不同时间的样品以100mm min-1的加载速率进行拉伸测试，发现修复1min的样品就可以被拉伸2倍，修复5min的样品可以被拉伸6倍，测试结果参见图10。
分析例9
(1)用实施例2中步骤(1)中得到的均匀分散液制备成特定形状的样品，再通过光固化拼接得到一个长方体的气动模型，其外部轮廓为长×宽×高为23mm×17mm×6mm，其内部空腔为长×宽×高为15mm×9mm×4mm。
(2)使用针筒在(1)中的空腔内充入50mL空气，拔出针头后该模型可快速修复密封。
(3)使用针头扎破(2)中充气后的气动模型，仅经过修复几秒后，该气动模型又可以充入50mL空气且保持密封。
5.聚电解质凝胶气球的抗冲击性
分析例10
(1)用实施例2中步骤(1)中得到的均匀分散液制备成特定形状的样品，再通过光固化拼接得到一个长方体的气动模型，其外部轮廓为长×宽×高为23mm×17mm×6mm，其内部空腔为长×宽×高为15mm×9mm×4mm。
(2)使用针筒在(1)中的空腔内充入50mL空气，拔出针头后该模型可快速修复密封。
(3)将(2)中充气后的气动模型放在拉力机下进行压缩应力-应变测试，模型高度可被压缩80％并承受大于100N的压力而不发生破裂，参见图11，并且在移除外力后迅速反弹到原状。
分析例11
(1)用实施例2中步骤(1)中得到的均匀分散液制备成特定形状的样品，再通过光固化拼接得到一个立方体的气动模型，其外部轮廓为长×宽×高为40mm×40mm×40mm，其内部空腔为长×宽×高为30mm×30mm×30mm。
(2)使用针筒在(1)中的空腔内充入2700mL空气，拔出针头后该模型可快速修复密封。
(3)将(2)中充气后的气动模型(体积变化约100倍)可承受成年人的重量而不破裂，并在移除外力后立即反弹。
工业可适用性
本公开实施例提供的聚电解质凝胶的制备方法简单，制得的聚电解质凝胶具有优异的拉伸性能与弹性性能；同时本公开实施例的聚电解质凝胶具有优异的快修复性能，可以迅速修复各种小的机械损伤，包括针刺、切割等；本公开实施例的聚电解质凝胶还具有优异的离子导电性，为自体体积传感与外界感知打下基础；基于本公开实施例的聚电解质凝胶得到的气球还有优异的抗冲击性能。综上所述，本公开实施例的聚电解质凝胶以及其设计思路在软体机器人，超弹性电极，药物输送载体，组织工程支架，生物电子，伤口敷料，隐形眼镜，电 池和超级电容器，光学设备，声学设备，能量转换器，生物粘合剂，涂层，医疗美容、超高分辨率打印等领域有着广泛的应用前景。
此外，在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (18)

  1. 一种聚电解质凝胶，其中，所述聚电解质凝胶的原料包含聚电解质单体和溶剂，所述聚电解质单体具有亲溶剂的离子基团与疏溶剂且柔性的非离子基团，通过调节溶剂极性与溶剂含量，在远程静电相互作用和短程疏溶剂相互作用的拮抗与平衡下，聚电解质链发生不均匀溶剂化，使所述聚电解质形成串珠结构。
  2. 根据权利要求1所述的聚电解质凝胶，其中，所述溶剂具有亲水性，选用水、乙二醇和丙三醇中的任意一种或多种的混合物。
  3. 根据权利要求1所述的聚电解质凝胶，其中，所述聚电解质的单体中，所述亲溶剂的离子基团为易溶于水的离子基团，所述疏溶剂且柔性的非离子基团为聚乙二醇链、碳链或硅氧烷链。
  4. 根据权利要求1所述的聚电解质凝胶，其中，所述聚电解质的结构式为-[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-和-[Si(OR)2-O-(B)b]n-中的任意一种，n为聚合度，n≧2，(B)b为-[CH2CH2O]b-，b≥0，R为以下任意一种或多种含离子的有机侧链且要求所选的多种含离子的有机侧链之间不发生聚沉：
    R由聚阳离子链段-(M)m-A1+-(L)l(CH3)k和游离对离子B1-构成,M可为-CH2-或-CH2CH2O-，L可为-CH2-或-CH2CH2O-，m、l、k均为重复单元数，1≤m≤5，0≤l≤5,0≤k≤1；A1+为有机阳离子，包括季铵盐、季鏻盐、咪唑和吡啶鎓阳离子；B1-为阴离子，包括氟、氯、溴、碘、磷酸根、磺酸根、羧酸根和硫酸根；
    R由聚阴离子链段-(P)p-B2--(Q)q(CH3)r和游离对离子为A2+构成，P可为-CH2-或-CH2CH2O-，Q可为-CH2-或-CH2CH2O-，p、q、r均为重复单元数，1≤p≤5，0≤q≤5,0≤r≤1；A2+为金属或有机阳离子，包括锂、钠、钾、镁、钙、钡、锌、银、铁、铝、铜、季铵盐、季鏻盐、咪唑和吡啶鎓阳离子；B2-为阴离子，包括磺酸根、羧酸根、磷酸根和硫酸根；
    R为聚两性离子链段-(X)x-A3+-(Y)y-B3--(Z)z(CH3)w或-(X)x-B3--(Y)y-A3+-(Z)z(CH3)w，X为-CH2-或-CH2CH2O-，Y为-CH2-或-CH2CH2O-，Z为-CH2-或-CH2CH2O-，x、y、z、w均为重复单元数，1≤x≤5，1≤y≤5，0≤z≤5,0≤w≤1；A3+为有机阳离子，包括季铵盐、季鏻盐、咪唑和吡啶鎓阳离子；B3-为阴离子，包括磺酸根、羧酸根、磷酸根和硫酸根。
  5. 根据权利要求1所述的聚电解质凝胶，其中，所述聚电解质选用以下任意一种或多种彼此之间不会发生聚沉的电解质单体：(2-丙烯酰氧基乙基)三甲基氯化铵、(2-丙烯酰氧基乙基)三甲基溴化铵、(2-丙烯酰氧基乙基)三甲基碘化铵、(3-丙烯酰氧基丙基)三甲基氯化铵、(3-丙烯酰氧基丙基)三甲基溴化铵、(3-丙烯酰氧基丙基)三甲基碘化铵、(2-丙烯酰氧基丁基)三甲基氯化铵、(2-丙烯酰氧基丁基)三甲基溴化铵、(2-丙烯酰氧基丁基)三甲基碘化铵、(3-丙烯酰胺丙基)三甲基氯化铵、(3-丙烯酰胺丙基)三甲基溴化铵、(3-丙烯酰胺丙基)三甲基碘化铵、(2-丙烯酰胺丁基)三甲基氯化铵、(2-丙烯酰胺丁基)三甲基溴化铵、(2-丙烯酰胺丁基)三甲基碘化铵、(5-丙烯酰氨基戊基)三甲基氯化铵、(5-丙烯酰氨基戊基)三甲基溴化铵、(5-丙烯酰氨基戊基)三甲基碘化铵、丙烯酸3-磺丙酯钾盐、丙烯酸3-磺丙酯钠盐、丙烯酸3-磺丙酯锂盐、丙烯酸2-磺乙酯钠盐、丙烯酸2-磺乙酯钾盐、丙烯酸2-磺乙酯锂盐、丙烯酸4-磺丁酯钾盐、丙烯酸4-磺丁酯钠盐、丙烯酸4-磺丁酯锂盐、丙烯酰胺2-磺乙酯钠盐、丙烯酰胺2-磺乙酯钾盐、丙烯酰胺2-磺乙酯锂盐、丙烯酰胺3-磺 丙酯钾盐、丙烯酰胺3-磺丙酯钠盐、丙烯酰胺3-磺丙酯锂盐、丙烯酰胺4-磺丁酯钾盐、丙烯酰胺4-磺丁酯钠盐、丙烯酰胺4-磺丁酯锂盐、丙烯酰氧乙基磺基甜菜碱、丙烯酰氧乙基二甲基铵丙酸酯、丙烯酰胺丙基二甲基铵乙酸酯和丙烯酰氧乙基磷酸胆碱。
  6. 根据权利要求1所述的聚电解质凝胶，其中，所述聚电解质凝胶通过含有乙烯双键的电解质单体或硅氧烷电解质或聚乙二醇电解质、溶剂、引发剂的均匀混合溶液在紫外光照或加热下发生自由基聚合制备。
  7. 根据权利要求1所述的聚电解质凝胶，其中，所述聚电解质凝胶的原料还包括引发剂，所述引发剂为光引发剂，选自2-羟基-2-甲基丙二酮、2-氧代戊二酸、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、2,4,6(三甲基苯甲酰基)二苯基氧化膦、三氟甲磺酰酯、三乙磷酸二苯基二唑和二苯基乙烯二胺中的至少一种；或者所述引发剂为热引发剂，选自过硫酸铵、过硫酸钾、过硫酸钠和过氧化二甲苯酰中的至少一种。
  8. 根据权利要求1所述的聚电解质凝胶，其中，所述聚电解质凝胶的原料还包括化学交联剂，所述化学交联剂选用聚乙二醇二丙烯酸酯、(八氢-4,7-亚甲基-1H-茚-1,5-亚基)双(亚甲基)二丙烯酸酯、N,N-亚甲基双丙烯酰胺、聚乙二醇二甲基丙烯酸酯、二甲基丙烯酸乙二醇酯、(甲基)丙烯酸乙烯氧基聚乙二醇酯和6,6'-双氨基-3,3'-甲叉基二苯甲酸中的至少一种。
  9. 根据权利要求8所述的聚电解质凝胶，其中，所述化学交联剂的含量为相对于所述聚电解质单体0-0.01个当量。
  10. 根据权利要求1～9中任一项所述的聚电解质凝胶，其中，所述聚电解质与溶剂分子的摩尔比为1:2.5～1:12。
  11. 根据权利要求10所述的聚电解质凝胶，其中，所述聚电解质单体与所述溶剂分子的摩尔比优选在1:3-1:8之间。
  12. 根据权利要求10所述的聚电解质凝胶，其中，所述聚电解质凝胶具有各向同性，且具有700％～1500％的可逆单轴应变和3000％～10,000％的可逆双轴面应变。
  13. 根据权利要求10所述的聚电解质凝胶，其中，所述聚电解质凝胶经5min修复后的应变可达到初始应变的20％。
  14. 一种根据权利要求1～13中任一项所述聚电解质凝胶的制备方法，包括：
    将聚电解质单体、溶剂、引发剂以及可选的交联剂，在室温下混合搅拌，使其均匀分散以获得均匀分散液；
    所述均匀分散液固化成型，得到所述聚电解质凝胶。
  15. 根据权利要求14所述的方法，其中，所述均匀分散液在温度25±3℃、湿度30±15％的条件下通过紫外光照或加热固化成型。
  16. 根据权利要求15所述的方法，其中，所述引发剂为光引发剂，选自2-羟基-2-甲基丙二酮、2-氧代戊二酸、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、2,4,6(三甲基苯甲酰基)二苯基氧化膦、三氟甲磺酰酯、三乙磷酸二苯基二唑和二苯基乙烯二胺中的至少一种；或者引发剂为热引发剂，选自过硫酸铵、过硫酸钾、过硫酸钠和过氧化二甲苯酰中的至少一种。
  17. 根据权利要求14～15中任一项所述的方法，其中，所述交联剂为聚乙二醇二丙烯酸酯、(八氢-4,7-亚甲基-1H-茚-1,5-亚基)双(亚甲基)二丙烯酸酯、N,N-亚甲基双丙烯酰胺、聚乙二醇二甲基丙烯酸酯、二甲基丙烯酸乙二醇酯、(甲基)丙烯酸乙烯氧基聚乙二醇酯和6,6' -双氨基-3,3'-甲叉基二苯甲酸中的至少一种。
  18. 一种根据权利要求1～13中任一项所述的聚电解质凝胶和/或权利要求14～17中任一项所述的方法制得的聚电解质凝胶在软体机器人、生物医药、医疗美容、柔性可穿戴设备和超高分辨率打印中的应用。
PCT/CN2023/112030 2023-06-16 2023-08-09 聚电解质凝胶及其制备方法和应用 Ceased WO2024254965A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202310715758.2A CN117024774A (zh) 2023-06-16 2023-06-16 聚电解质凝胶及其制备方法和应用
CN202310715758.2 2023-06-16

Publications (1)

Publication Number Publication Date
WO2024254965A1 true WO2024254965A1 (zh) 2024-12-19

Family

ID=88640083

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/112030 Ceased WO2024254965A1 (zh) 2023-06-16 2023-08-09 聚电解质凝胶及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN117024774A (zh)
WO (1) WO2024254965A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120271748A (zh) * 2025-03-18 2025-07-08 佛山职业技术学院 一种高灵敏度拉伸-压力双模响应的水凝胶及其制备方法及应用

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104262880A (zh) * 2014-09-11 2015-01-07 江南大学 一种高强度抑菌纳米复合阳离子双网络水凝胶及其制备方法
KR20180000195A (ko) * 2016-06-22 2018-01-02 울산과학기술원 복합 전해질, 그 제조방법, 및 이를 포함하는 이차 전지
CN108257785A (zh) * 2017-12-19 2018-07-06 中南大学 光固化的凝胶离子液体电解质及其制备方法、铝电解电容器
WO2021107437A1 (ko) * 2019-11-28 2021-06-03 한국재료연구원 3d 프린팅용 자가 치유 이온 전도성 젤 조성물
CN114349899A (zh) * 2021-12-10 2022-04-15 深圳大学 一种自粘附导电凝胶及其制备方法
CN114456308A (zh) * 2022-02-28 2022-05-10 华中科技大学 一种光热水凝胶、制备方法及其应用、光热转化蒸发器
CN114736393A (zh) * 2022-03-01 2022-07-12 浙江清华柔性电子技术研究院 导电水凝胶及其制备方法和应用
US20220396672A1 (en) * 2019-10-23 2022-12-15 Korea University Research And Business Foundation Organic ionic conductive polymer gel elastomer and method for preparing same
CN115678049A (zh) * 2021-07-29 2023-02-03 江南大学 一种高强度耐高温柔性凝胶电解质的制备方法
CN115819684A (zh) * 2022-11-25 2023-03-21 中国科学院宁波材料技术与工程研究所 一种多功能离子导电型高强韧水凝胶及其制备方法和应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8673503B2 (en) * 2010-06-04 2014-03-18 Indian Institute Of Technology Bombay Polyurethane gel electrolytes with improved conductance and/or solvent retention

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104262880A (zh) * 2014-09-11 2015-01-07 江南大学 一种高强度抑菌纳米复合阳离子双网络水凝胶及其制备方法
KR20180000195A (ko) * 2016-06-22 2018-01-02 울산과학기술원 복합 전해질, 그 제조방법, 및 이를 포함하는 이차 전지
CN108257785A (zh) * 2017-12-19 2018-07-06 中南大学 光固化的凝胶离子液体电解质及其制备方法、铝电解电容器
US20220396672A1 (en) * 2019-10-23 2022-12-15 Korea University Research And Business Foundation Organic ionic conductive polymer gel elastomer and method for preparing same
WO2021107437A1 (ko) * 2019-11-28 2021-06-03 한국재료연구원 3d 프린팅용 자가 치유 이온 전도성 젤 조성물
CN115678049A (zh) * 2021-07-29 2023-02-03 江南大学 一种高强度耐高温柔性凝胶电解质的制备方法
CN114349899A (zh) * 2021-12-10 2022-04-15 深圳大学 一种自粘附导电凝胶及其制备方法
CN114456308A (zh) * 2022-02-28 2022-05-10 华中科技大学 一种光热水凝胶、制备方法及其应用、光热转化蒸发器
CN114736393A (zh) * 2022-03-01 2022-07-12 浙江清华柔性电子技术研究院 导电水凝胶及其制备方法和应用
CN115819684A (zh) * 2022-11-25 2023-03-21 中国科学院宁波材料技术与工程研究所 一种多功能离子导电型高强韧水凝胶及其制备方法和应用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120271748A (zh) * 2025-03-18 2025-07-08 佛山职业技术学院 一种高灵敏度拉伸-压力双模响应的水凝胶及其制备方法及应用

Also Published As

Publication number Publication date
CN117024774A (zh) 2023-11-10

Similar Documents

Publication Publication Date Title
Di et al. Bioinspired, nucleobase-driven, highly resilient, and fast-responsive antifreeze ionic conductive hydrogels for durable pressure and strain sensors
Bilici et al. Melt-processable shape-memory hydrogels with self-healing ability of high mechanical strength
Liu et al. Tough and responsive oppositely charged nanocomposite hydrogels for use as bilayer actuators assembled through interfacial electrostatic attraction
Peak et al. A review on tough and sticky hydrogels
Zhao et al. Reactive macromolecular micelle crosslinked highly elastic hydrogel with water-triggered shape-memory behaviour
Nakajima et al. Tough double-network gels and elastomers from the nonprestretched first network
CN115368509A (zh) 一种自愈、抗冻、自粘性且具有双折射特性的导电离子水凝胶及其制备方法与应用
Chen et al. Highly stretchable, self-healing, and 3D printing prefabricatable hydrophobic association hydrogels with the assistance of electrostatic interaction
Liu et al. Flexible strain sensors with rapid self-healing by multiple hydrogen bonds
KR102010993B1 (ko) 3성분으로 구성된 pa 하이드로겔
Zhu et al. Processing tough supramolecular hydrogels with tunable strength of polyion complex
CN104448153B (zh) 一种含磷酸胆碱的高强度聚氨酯水凝胶及其制备方法
CN113527714B (zh) 一种抗冻导电水凝胶及其制备方法和力响应传感应用
CN115819684A (zh) 一种多功能离子导电型高强韧水凝胶及其制备方法和应用
CN108752370A (zh) 基于动态共价交联剂的可拉伸自修复水凝胶及其制备方法
Zhang et al. A graphene hybrid supramolecular hydrogel with high stretchability, self-healable and photothermally responsive properties for wound healing
Li et al. Frontal polymerization-oriented self-healing hydrogels and applications toward temperature-triggered actuators
Liu et al. Highly stretchable, self-adhesive, ambient-stable, and wide-temperature adaptable hydrophobic ionogels for wearable strain sensors
CN110527036A (zh) 具有水响应双向可逆形状记忆功能的高分子材料及其制备方法
Wang et al. Poly (N, N-dimethyl) acrylamide-based ion-conductive gel with transparency, self-adhesion and rapid self-healing properties for human motion detection
CN111848982A (zh) 一种自愈合导电离子凝胶及其制备方法与应用
Liang et al. Nature-inspired semi-IPN hydrogels with tunable mechanical properties and multi-responsiveness
CN117024774A (zh) 聚电解质凝胶及其制备方法和应用
CN116496443A (zh) 一种全固态离子导电弹性体及其制备方法
Li et al. Nanocellulose-toughened super-stretchable ionic conductive gel fibers for wearable strain sensors

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23941191

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE