A high-mechanical-strength ion-conducting elastomer based on a triple interpenetrating network and a preparation method and application thereof

Abstract

This invention relates to the field of flexible ion-conducting materials technology, and discloses a high-mechanical-strength ion-conducting elastomer based on a triple interpenetrating network, its preparation method, and its application. The method includes: first, mixing acrylamide thiolactone, ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, and polyethylene glycol diacrylate with a eutectic solvent, adding a photo / thermal initiator, and curing under UV or thermopolymer to obtain elastomer A. Then, it is laterally stretched and oriented, and a diamine is added to react with the thiolactone to fix the orientation structure. Subsequently, it is immersed in a mixture containing ethylene glycol methyl ether acrylate, polyethylene glycol diacrylate, fluorinated acrylate, lithium salt, and an initiator, swelling to constant weight and then curing. This is followed by a second swelling-curing process to construct a triple interpenetrating network. This method, through stretching and orientation and two swelling-curing cycles, effectively balances the material's mechanical properties, conductivity, and sensitivity. The resulting elastomer exhibits excellent overall performance and is suitable for the field of flexible electronic sensors.

Description

Technical Field

[0001] This invention relates to the field of flexible ion-conducting materials technology, and more specifically, to a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network, its preparation method, and its application. Background Technology

[0002] With the rapid development of flexible electronics fields such as wearable electronic devices, human-computer interaction, and soft robots, conductive elastomers have become an indispensable part of this field. Therefore, designing conductive elastomers with high mechanical strength, high resilience, environmental friendliness, long-term stability, and durability has become the foundation for the development of flexible electronics. To meet these stringent requirements, ionic conductors possess high ionic conductivity, high sensitivity, and adjustable strain.

[0003] However, existing ion-conductive elastic hydrogels and organic gels suffer from solvent evaporation, ionic liquid leakage, the trade-off between mechanical strength and conductivity, and insufficient elastic recovery and fatigue resistance, making it difficult to maintain stability during long-term use. Ionic gels, composed of polymer networks and ion-conductive fillers, inherit the excellent properties of ionic liquids (such as high ionic conductivity and high sensitivity) and polymer networks (tunable mechanical properties, deformability, and high resilience), making them more stable than hydrogels and organic gels, and thus have been widely studied. However, in ionic gels, the ionic liquid acts as a plasticizer and is prone to leakage, making it difficult to balance the mechanical strength and ionic conductivity of the conductive elastomer. Currently, ionic gels with high conductivity are typically characterized by low modulus (<0.1 MPa) and tensile strength <1 MPa, exhibiting large hysteresis loops after cyclic stretching and slow mechanical property recovery, making them susceptible to damage during use and causing signal transmission distortion, which severely limits their application range. The combination of polymers and nanofillers can effectively improve the mechanical strength of elastomers, but creep is prone to occur during use, which can severely damage the various properties of the material and reduce the light transmittance of the final conductive elastomer.

[0004] To improve the mechanical strength of ionicly conductive elastomers and prevent ionic liquid leakage, solid metal salts (such as lithium trifluoromethanesulfonate imine salt) are directly added to the elastomer. While the all-solid nature effectively solves the problems of ionic liquid leakage and severe reduction in mechanical strength, fatigue damage is prone to occur during cyclic tensile testing. Furthermore, in conductive elastomers with the same ion content, the conductivity of elastomers containing lithium trifluoromethanesulfonate imine salt is significantly lower than that of elastomers containing ionic liquids.

[0005] Therefore, providing an ion-conductive elastomer with high electrical conductivity, high mechanical strength, fatigue resistance, and high stability is of great significance for meeting its practical application requirements. Summary of the Invention

[0006] In view of this, the present invention proposes a high mechanical strength ion-conductive elastomer based on a triple interpenetrating network, its preparation method and application, aiming to solve at least one of the current background technical problems.

[0007] This invention proposes a method for preparing a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network, comprising the following steps: Step 1: Mix acrylamide thiolactone, ethylene glycol methyl ether acrylate, fluorinated acrylate or long-chain alkane acrylate, polyethylene glycol diacrylate, and initiator in a molar ratio of 2~10:15~30:15~30:0.5~2:0.01~0.1 to obtain a mixed system. Then, mix the eutectic solvent with the mixed system in a mass ratio of 0.1~0.5:1. After thorough mixing, pour the mixture into a mold for photocuring or thermocuring to prepare ion-conductive elastomer A. Step 2: The ion-conducting elastomer A is stretched laterally to a strain of 10%~20%, and then diamine is added to react and obtain ion-conducting elastomer A with fixed orientation. Step 3: The fixed-orientation ion-conductive elastomer A is placed in the first mixed solution for swelling. When the swollen fixed-orientation ion-conductive elastomer A reaches a constant weight, it is photocured or thermocured to obtain a conductive elastomer with a dual network. Step 4: Place the conductive elastomer with dual networks in the second mixed solution for further swelling. After swelling, when the weight reaches constant, perform photocuring or thermal curing to obtain the triple interpenetrating network high mechanical strength ion-conductive elastomer. The first and second mixed solutions are both obtained by mixing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate, an initiator, and a lithium salt. The ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, and polyethylene glycol diacrylate are polymer monomers. The molar ratio of ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate, and the initiator is 20~30:10~20:30~40:0.01~0.1, and the mass ratio of lithium salt to total polymer monomers is 0.1~0.5:1.

[0008] Preferably, the acrylamide thiolactone in step 1 is methacrylamide thiolactone or acrylamide thiolactone. The fluorinated acrylate is one of trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, tridecyl fluorooctyl acrylate, tridecyl fluorooctyl methacrylate, and heptadecafluorodecyl methacrylate. The long-chain alkane-containing acrylate is one of dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, and dodecyl acrylate; The polyethylene glycol diacrylate is one of polyethylene glycol diacrylate (Mn~400), polyethylene glycol diacrylate (Mn~575), polyethylene glycol diacrylate (Mn~700), and polyethylene glycol diacrylate (Mn~1000).

[0009] Preferably, the eutectic solvent in step 1 is any of the following systems: A: Choline chloride and zinc chloride are mixed at a mass ratio of 1:2; B: Choline chloride and zinc chloride are mixed at a mass ratio of 1:3; C: Choline chloride and zinc chloride monohydrate are mixed at a mass ratio of 1:2; D: Choline chloride and ferric chloride hexahydrate are mixed at a mass ratio of 1:2; E: Choline chloride and urea are mixed at a mass ratio of 1:2; F: Choline chloride and glycerol are mixed in a mass ratio of 1:2; G: Choline chloride and ethylene glycol are mixed at a mass ratio of 1:2; H: Choline chloride and lactic acid are mixed in a mass ratio of 1:2; I: Triethanolamine and lactic acid are mixed at a mass ratio of 1:2.

[0010] Preferably, the initiator in steps 1 and 3 includes an ultraviolet photoinitiator and a thermal initiator, wherein the photoinitiator is one or a combination of several of the following: 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 1-hydroxycyclohexylphenyl ketone (184), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), 2-methyl-2-(4-morpholino)-1-[4-(methylthio)phenyl]-1-propanone (907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (369), methyl benzoylformate (MBF), benzophenone (BP), aryl iodomonium salts, and mixed triaryl thiomonium salts; The thermal initiator is one or a combination of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), and tert-butyl peroxide-2-ethylhexanoate.

[0011] Preferably, the diamine in step 2 is one or a combination of cystamine, 1,6-hexanediamine, and ethylenediamine.

[0012] Preferably, the ethylene glycol methyl ether acrylate and polyethylene glycol diacrylate mentioned in step 3 are the same as those in step 1; The hydroxyethyl acrylate includes hydroxyethyl acrylate and hydroxyethyl methacrylate; The lithium salt mentioned in step 3 is one or a combination of lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonyl-perfluorobutylsulfonylimide, lithium trifluoromethanesulfonyl-perfluoropropylsulfonylimide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluoroborate oxalate, lithium difluorophosphate, lithium 4,5-dicyano-2-trifluoromethylimidazolium, and lithium chloride.

[0013] Preferably, the ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate, lithium salt, and initiator mentioned in step 4 are the same as those in step 3.

[0014] Preferably, in steps 1, 3, and 4, the ultraviolet lamp used for photocuring has a wavelength of 350nm and an irradiation time of 2min to 30min; when using thermal curing, the initiation temperature is 60 to 80℃.

[0015] The present invention also provides a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network, wherein the high mechanical strength ion-conducting elastomer based on a triple interpenetrating network is prepared by the preparation method described in the above technical solution.

[0016] The present invention also provides an application of the high mechanical strength ion-conductive elastomer based on the triple interpenetrating network described in the above technical solution, specifically its application in flexible electronic sensors.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention prepares an ion-conducting elastomer with a triple interpenetrating network structure through post-crosslinking of the polymer network and two-stage stretching-orientation-swelling-curing. By adjusting the type and ratio of the polymer monomers used to synthesize the ion-conducting elastomer, the type of eutectic solvent, and the lithium salt content, this invention regulates the mechanical properties, conductivity, sensitivity, hydrophobicity, and high / low temperature resistance of the final ion-conducting elastomer. It provides a method for preparing an ion-conducting elastomer that combines high mechanical strength, high sensitivity, fatigue resistance, high / low temperature resistance, and hydrophobicity, laying a solid foundation for the practical application of ion-conducting elastomers. Attached Figure Description

[0018] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings: Figure 1 This is a schematic diagram of the polymer molecular structure and ion-conducting elastomer structure of the triple interpenetrating network high mechanical strength ion-conducting elastomer in Example 1.

[0019] Figure 2This is a mechanical strength diagram of the high mechanical strength ion-conducting elastomer with a triple interpenetrating network in Example 1. Figure 3 This is a cyclic tensile curve of the high mechanical strength ion-conducting elastomer with triple interpenetrating network of the present invention. Figure 4 The figure shows the sensing stability test results of the high mechanical strength ion-conducting elastomer with triple interpenetrating network of the present invention. Detailed Implementation

[0020] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0021] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included within this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0022] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0023] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0024] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0025] This invention provides a method for preparing a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network, comprising the following steps: Step 1: Mix acrylamide thiolactone, ethylene glycol methyl ether acrylate, fluorinated acrylate or long-chain alkane acrylate, polyethylene glycol diacrylate, and initiator in a molar ratio of 2~10:15~30:15~30:0.5~2:0.01~0.1 to obtain a mixed system. Then, mix the eutectic solvent with the mixed system in a mass ratio of 0.1~0.5:1. After thorough mixing, pour the mixture into a mold for photocuring or thermocuring to prepare ion-conductive elastomer A. Specifically: the acrylamide thiolactone mentioned above is methacrylamide thiolactone or acrylamide thiolactone; The fluorinated acrylate is one of trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, tridecyl fluorooctyl acrylate, tridecyl fluorooctyl methacrylate, and heptadecafluorodecyl methacrylate. The long-chain alkane-containing acrylate is one of dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, and dodecyl acrylate; The polyethylene glycol diacrylate is one of polyethylene glycol diacrylate (Mn~400), polyethylene glycol diacrylate (Mn~575), polyethylene glycol diacrylate (Mn~700), and polyethylene glycol diacrylate (Mn~1000).

[0026] The eutectic solvent is any of the following systems: A: Choline chloride and zinc chloride are mixed at a mass ratio of 1:2; B: Choline chloride and zinc chloride are mixed at a mass ratio of 1:3; C: Choline chloride and zinc chloride monohydrate are mixed at a mass ratio of 1:2; D: Choline chloride and ferric chloride hexahydrate are mixed at a mass ratio of 1:2; E: Choline chloride and urea are mixed at a mass ratio of 1:2; F: Choline chloride and glycerol are mixed in a mass ratio of 1:2; G: Choline chloride and ethylene glycol are mixed at a mass ratio of 1:2; H: Choline chloride and lactic acid are mixed in a mass ratio of 1:2; I: Triethanolamine and lactic acid are mixed at a mass ratio of 1:2.

[0027] Step 2: The ion-conducting elastomer A is stretched laterally to a strain of 10%~20%, and then diamine is added to react and obtain ion-conducting elastomer A with fixed orientation. Specifically, the diamine is one or a combination of cystamine, 1,6-hexanediamine, and ethylenediamine, and the amount of the diamine used is such that its molar ratio with that of the thiolactone in the polymer is 0.5:1.

[0028] Step 3: The fixed-orientation ion-conductive elastomer A is placed in the first mixed solution for swelling. When the swollen fixed-orientation ion-conductive elastomer A reaches a constant weight, it is photocured or thermocured to obtain a conductive elastomer with a dual network. Specifically: the initiators mentioned in steps 1 and 3 both include ultraviolet photoinitiators and thermal initiators. The photoinitiator is preferably one or a combination of several of the following: 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 1-hydroxycyclohexylphenyl ketone (184), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), 2-methyl-2-(4-morpholino)-1-[4-(methylthio)phenyl]-1-propanone (907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (369), methyl benzoylformate (MBF), benzophenone (BP), aryl iodomonium salts, and mixed triaryl thiomonium salts. The thermal initiator is preferably one or a combination of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), and tert-butyl peroxide-2-ethylhexanoate.

[0029] The ethylene glycol methyl ether acrylate and polyethylene glycol diacrylate are the same as those in step 1; The hydroxyethyl acrylate includes hydroxyethyl acrylate and hydroxyethyl methacrylate; The lithium salt is preferably one or a combination of lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonyl-perfluorobutylsulfonylimide, lithium trifluoromethanesulfonyl-perfluoropropylsulfonylimide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluoroborate oxalate, lithium difluorophosphate, lithium 4,5-dicyano-2-trifluoromethylimidazolium, and lithium chloride.

[0030] Step 4: Place the conductive elastomer with dual networks in the second mixed solution for further swelling. After swelling, when the weight reaches constant, perform photocuring or thermal curing to obtain the triple interpenetrating network high mechanical strength ion-conductive elastomer. Specifically, the ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate, lithium salt, and initiator mentioned in step 4 are the same as those in step 3.

[0031] In steps 1, 3, and 4, the wavelength of the ultraviolet lamp used for photocuring is preferably 350 nm, and the irradiation time is preferably 2 min to 30 min; when using thermal curing, the initiation temperature is preferably 60 to 80 °C.

[0032] Furthermore, in the above technical solution, both the first and second mixed solutions are obtained by mixing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate, an initiator, and a lithium salt; the ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, and polyethylene glycol diacrylate are polymer monomers, the molar ratio of ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate, and the initiator is 20~30:10~20:30~40:0.01~0.1, and the mass ratio of lithium salt to the total polymer monomers is 0.1~0.5:1.

[0033] The present invention also provides a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network, wherein the high mechanical strength ion-conducting elastomer based on a triple interpenetrating network is prepared by the preparation method described in the above technical solution.

[0034] The present invention also provides an application of the high mechanical strength ion-conductive elastomer based on the triple interpenetrating network described in the above technical solution, specifically its application in flexible electronic sensors.

[0035] Example 1 Step 1: Acrylamide thiolactone, ethylene glycol methyl ether acrylate, hexafluorobutyl acrylate, polyethylene glycol diacrylate (Mn~400), and azobisisobutyronitrile (AIBN) were mixed in a molar ratio of 2:30:30:0.5:0.01. A eutectic solvent (choline chloride: zinc chloride (1:2)) was added to the total polymer monomers in a mass ratio of 0.1. After thorough mixing, the mixture was poured into a 1mm×50mm×50mm mold and kept at 70℃ for 3 hours to prepare ion-conductive elastomer A.

[0036] Step 2: The ion-conductive elastomer A prepared in Step 1 is stretched laterally to a strain of 10%. Then, 1,6-hexanediamine with a molar ratio of 0.5 to thiolactone in the polymer is added to react with the thiolactone in the elastomer network to fix the orientation structure. Step 3: Immerse the fixed-orientation ion-conducting elastomer A in a mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate (Mn~575) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) in a molar ratio of 20:10:40:0.05, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.3. When the swollen ion-conducting elastomer reaches constant weight, irradiate it under ultraviolet light (365nm) for 5 minutes to obtain a conductive elastomer with a dual network. Step 4: The swollen and cured elastomer was further swollen in a homogeneous mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) in a molar ratio of 30:15:30:0.04, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.5. After swelling and reaching constant weight, it was irradiated under ultraviolet light (365nm) for 5 minutes to obtain a triple interpenetrating network high mechanical strength ion-conducting elastomer.

[0037] Example 2 Step 1: Acrylamide thiolactone, ethylene glycol methyl ether acrylate, hexafluorobutyl methacrylate, polyethylene glycol diacrylate (Mn~575), and azobisisobutyronitrile (AIBN) are mixed in a molar ratio of 3:30:30:0.5:0.01, with a eutectic solvent (choline chloride: zinc chloride (1:3)) and a total polymer monomer mass ratio of 0.2. After thorough mixing, the mixture is poured into a 1mm×50mm×50mm mold and kept at 70℃ for 3h to prepare ion-conductive elastomer A. Step 2: The ion-conductive elastomer A prepared in Step 1 is stretched laterally to a strain of 10%. Then, cystamine with a molar ratio of 0.5 to thiolactone in the polymer is added to react with the thiolactone in the elastomer network to fix the orientation structure, thus fixing the orientation of the ion-conductive elastomer A. Step 3: Immerse the fixed-orientation ion-conducting elastomer A in a mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate (Mn~700) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) in a molar ratio of 20:10:40:0.05, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.3. When the swollen ion-conducting elastomer reaches constant weight, irradiate it under ultraviolet light (365nm) for 5 minutes to obtain a conductive elastomer with a dual network. Step 4: The swollen and cured elastomer was further swollen in a homogeneous mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate (Mn~1000) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) in a molar ratio of 30:15:30:0.04, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.5. After swelling and reaching constant weight, it was irradiated with ultraviolet light (365 nm) for 5 min to obtain a triple interpenetrating network high mechanical strength ion-conducting elastomer.

[0038] Example 3 Step 1: Acrylamide thiolactone, ethylene glycol methyl ether acrylate, tridecyl fluorooctyl acrylate, polyethylene glycol diacrylate (Mn~400), and benzoyl peroxide (BPO) were mixed in a molar ratio of 4:30:30:1:0.01. A eutectic solvent (choline chloride: urea (1:2)) and a total polymer monomer mass ratio of 0.4 were added and thoroughly mixed. The mixture was then poured into a 1mm×50mm×50mm mold and kept at 70℃ for 3 hours to prepare ion-conductive elastomer A. Step 2: The ion-conducting elastomer A prepared in Step 1 is stretched laterally to a strain of 15%. Then, cystamine with a molar ratio of 0.5 to thiolactone in the polymer is added to react with the thiolactone in the elastomer network to fix the orientation structure, thus obtaining a fixed-orientation ion-conducting elastomer A. Step 3: Immerse the fixed-orientation ion-conducting elastomer A in a mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate (Mn~700), and 1-hydroxycyclohexylphenyl ketone (184) in a molar ratio of 20:10:40:0.05, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.3. When the swollen ion-conducting elastomer reaches constant weight, irradiate it under ultraviolet light (365nm) for 5 minutes to obtain a conductive elastomer with a dual network. Step 4: The swollen and cured elastomer was further swollen in a homogeneous mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate (Mn~575) and 1-hydroxycyclohexylphenyl ketone (184) in a molar ratio of 30:15:30:0.04, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.5. After swelling and reaching constant weight, it was irradiated under ultraviolet light (365nm) for 5 minutes to obtain a triple interpenetrating network high mechanical strength ion-conducting elastomer.

[0039] Example 4 Step 1: Acrylamide thiolactone, ethylene glycol methyl ether acrylate, tridecyl fluorooctyl acrylate, polyethylene glycol diacrylate (Mn~575), and benzoyl peroxide (BPO) were mixed in a molar ratio of 4:30:30:1:0.01. The total mass ratio of the eutectic solvent (choline chloride: glycerol (1:2)) to the total polymer monomers was 0.5. The mixture was poured into a 1mm×50mm×50mm mold and kept at 70℃ for 3h to prepare ion-conductive elastomer A. Step 2: The ion-conducting elastomer A prepared in Step 1 is stretched laterally to a strain of 20%. Then, ethylenediamine with a molar ratio of 0.5 to thiolactone in the polymer is added to react with the thiolactone in the elastomer network to fix the orientation structure, thus obtaining the ion-conducting elastomer A with fixed orientation. Step 3: Immerse the fixed-orientation ion-conducting elastomer A in a mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate (Mn~700) and 1-hydroxycyclohexylphenyl ketone (184) in a molar ratio of 20:10:40:0.05, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.3. When the swollen ion-conducting elastomer reaches constant weight, irradiate it under ultraviolet light (365nm) for 5 minutes to obtain a conductive elastomer with a dual network. Step 4: The swollen and cured elastomer was further swollen in a homogeneous mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate (Mn~1000) and 1-hydroxycyclohexylphenyl ketone (184) in a molar ratio of 30:15:30:0.04, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.5. After swelling and reaching constant weight, it was irradiated under ultraviolet light (365nm) for 5 minutes to obtain a triple interpenetrating network high mechanical strength ion-conducting elastomer.

[0040] Example 5 Step 1: Acrylamide thiolactone, ethylene glycol methyl ether acrylate, trifluoroethyl acrylate, polyethylene glycol diacrylate (Mn~575), and benzoyl peroxide (BPO) are mixed in a molar ratio of 4:30:30:1:0.01. A eutectic solvent (choline chloride: ethylene glycol (1:2)) is added to the total polymer monomers in a mass ratio of 0.5. After thorough mixing, the mixture is poured into a 1mm×50mm×50mm mold and kept at 70℃ for 3 hours to prepare ion-conductive elastomer A. Step 2: The ion-conducting elastomer A prepared in Step 1 is stretched laterally to a strain of 20%. Then, ethylenediamine with a molar ratio of 0.5 to thiolactone in the polymer is added to react with the thiolactone in the elastomer network to fix the orientation structure, thus obtaining the ion-conducting elastomer A with fixed orientation. Step 3: Immerse the fixed-orientation ion-conducting elastomer A in a mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate (Mn~700), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) in a molar ratio of 20:10:40:0.05, and lithium trifluoromethanesulfonyl-perfluoropropylsulfonylimide in a total mass ratio of 0.5 to the polymer monomers. When the swollen ion-conducting elastomer reaches constant weight, irradiate it under ultraviolet light (365nm) for 5 minutes to obtain a conductive elastomer with a dual network. Step 4: The swollen and cured elastomer was further swollen in a homogeneous mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate (Mn~1000) and 1-hydroxycyclohexylphenyl ketone (184) in a molar ratio of 30:20:40:0.05, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.5. After swelling and reaching constant weight, it was irradiated under ultraviolet light (365nm) for 5 minutes to obtain a triple interpenetrating network high mechanical strength ion-conducting elastomer.

[0041] Example 6 Step 1: Acrylamide thiolactone, ethylene glycol methyl ether acrylate, trifluoroethyl acrylate, polyethylene glycol diacrylate (Mn~1000), and benzoyl peroxide (BPO) are mixed in a molar ratio of 4:30:30:1:0.02, with a eutectic solvent (choline chloride: ethylene glycol (1:2)) and a total polymer monomer mass ratio of 0.5. After thorough mixing, the mixture is poured into a 1mm×50mm×50mm mold and kept at 70℃ for 3h to prepare ion-conductive elastomer A. Step 2: The ion-conducting elastomer A prepared in Step 1 is stretched laterally to a strain of 20%. Then, ethylenediamine with a molar ratio of 0.5 to thiolactone in the polymer is added to react with the thiolactone in the elastomer network to fix the orientation structure, thus obtaining the ion-conducting elastomer A with fixed orientation. Step 3: Immerse the fixed-orientation ion-conductive elastomer A in a mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate (Mn~700), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) in a molar ratio of 20:10:40:0.05, and lithium trifluoromethanesulfonyl-perfluoropropylsulfonylimide in a total mass ratio of 0.4 to the polymer monomers. When the swollen ion-conductive elastomer reaches constant weight, irradiate it under ultraviolet light (365nm) for 5 minutes to obtain a conductive elastomer with a dual network. Step 4: The swollen and cured elastomer was further swollen in a homogeneous mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate (Mn~400) and 1-hydroxycyclohexylphenyl ketone (184) in a molar ratio of 20:20:30:0.05, and lithium bis(trifluoromethanesulfonyl)imide to polymer monomers in a total mass ratio of 0.5. After swelling and reaching constant weight, it was irradiated under ultraviolet light (365nm) for 5 minutes to obtain a triple interpenetrating network high mechanical strength ion-conducting elastomer.

[0042] Example 7 Step 1: Acrylamide thiolactone, ethylene glycol methyl ether acrylate, octadecyl acrylate, polyethylene glycol diacrylate (Mn~1000), and benzoyl peroxide (BPO) were mixed in a molar ratio of 4:30:30:1:0.02. The total mass ratio of the eutectic solvent (choline chloride: zinc chloride (1:2)) to the polymer monomers was 0.5. The mixture was poured into a 1mm×50mm×50mm mold and kept at 70℃ for 3h to prepare ion-conductive elastomer A. Step 2: The ion-conducting elastomer prepared in Step 1 is stretched laterally to a strain of 20%. Then, ethylenediamine with a molar ratio of 0.5 to thiolactone in the polymer is added to react with the thiolactone in the elastomer network to fix the orientation structure, resulting in a fixed-orientation ion-conducting elastomer A. Step 3: Immerse the fixed-orientation ion-conducting elastomer A in a mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl methacrylate, polyethylene glycol diacrylate (Mn~700), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) in a molar ratio of 20:10:40:0.05, and a total mass ratio of lithium bis(fluorosulfonyl)imide to polymer monomers of 0.4. When the swollen ion-conducting elastomer reaches constant weight, irradiate it under ultraviolet light (365nm) for 5 minutes to obtain a conductive elastomer with a dual network.

[0043] Step 4: The swollen and cured elastomer was further swollen in a homogeneous mixture containing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate (Mn~400) and 1-hydroxycyclohexylphenyl ketone (184) in a molar ratio of 20:20:30:0.05, and lithium bis(fluorosulfonyl)imide to polymer monomers in a total mass ratio of 0.5. After swelling and reaching constant weight, it was irradiated under ultraviolet light (365nm) for 10 minutes to obtain a triple interpenetrating network high mechanical strength ion-conducting elastomer.

[0044] Performance testing Taking the sample obtained in Implementation Case 3 as an example, its mechanical properties and sensing properties are analyzed and characterized.

[0045] The mechanical properties of the material were characterized using a SANS CMT 8505 tensile testing machine. The distance between the clamps was 15 mm, and the tensile speed was 100 mm·min. -1 At least three spline samples were taken for each sample and tested. The average value of the test results was used to evaluate the mechanical properties of the sample. The results are as follows: Figure 2 and Figure 3 As shown, Figure 2 This is a diagram of the mechanical strength of the material. Figure 3 This is a cyclic tensile curve of the material, based on Figure 2 and Figure 3It can be seen that the prepared conductive elastomer has a mechanical strength of 6.5 MPa, and at the same time... Figure 3 This indicates that it has excellent resilience, which lays a good foundation for the mechanical properties of this material when used as a flexible electronic sensor material.

[0046] The resistance change (ΔR / R0) of the strain sensor was recorded using a Tektronix DMM 4040 6-1 / 2 digital precision multimeter. The measured sample was 10 mm long, 4 mm wide, and 0.5 mm thick, with a strain of 100%. The results are as follows: Figure 4 As shown in the test results, the material exhibits an ΔR / R0 value exceeding 100% at 100% strain, indicating excellent responsiveness. Furthermore, after 1000 cycles, the material maintains signal stability remarkably well. These combined excellent mechanical properties, electromechanical responsiveness, and signal stability lay a solid foundation for its practical applications.

[0047] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the specific implementation of the present invention. Any modifications or equivalent substitutions that do not depart from the spirit and scope of the present invention should be covered within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a high-mechanical-strength ion-conducting elastomer based on a triple interpenetrating network, characterized in that, Includes the following steps: Step 1: Mix acrylamide thiolactone, ethylene glycol methyl ether acrylate, fluorinated acrylate or long-chain alkane acrylate, polyethylene glycol diacrylate, and initiator in a molar ratio of 2~10:15~30:15~30:0.5~2:0.01~0.1 to obtain a mixed system. Then, mix the eutectic solvent with the mixed system in a mass ratio of 0.1~0.5:

1. After thorough mixing, pour the mixture into a mold for photocuring or thermocuring to prepare ion-conductive elastomer A. Step 2: The ion-conducting elastomer A is stretched laterally to a strain of 10%~20%, and then diamine is added to react and obtain ion-conducting elastomer A with fixed orientation. Step 3: The fixed-orientation ion-conductive elastomer A is placed in the first mixed solution for swelling. When the swollen fixed-orientation ion-conductive elastomer A reaches a constant weight, it is photocured or thermocured to obtain a conductive elastomer with a dual network. Step 4: Place the conductive elastomer with dual networks in the second mixed solution for further swelling. After swelling, when the weight reaches constant, perform photocuring or thermal curing to obtain the triple interpenetrating network high mechanical strength ion-conductive elastomer. The first and second mixed solutions are both obtained by mixing ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate, an initiator, and a lithium salt. The ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, and polyethylene glycol diacrylate are polymer monomers. The molar ratio of ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate, and the initiator is 20~30:10~20:30~40:0.01~0.1, and the mass ratio of lithium salt to total polymer monomers is 0.1~0.5:

1.

2. The method for preparing a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network according to claim 1, characterized in that, The fluorinated acrylate is one of trifluoroethyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, tridecyl fluorooctyl acrylate, tridecyl fluorooctyl methacrylate, and heptadecafluorodecyl methacrylate. The long-chain alkane-containing acrylate is one of dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, and dodecyl acrylate; The polyethylene glycol diacrylate is one of polyethylene glycol diacrylate (Mn~400), polyethylene glycol diacrylate (Mn~575), polyethylene glycol diacrylate (Mn~700), and polyethylene glycol diacrylate (Mn~1000).

3. The method for preparing a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network according to claim 1, characterized in that, The eutectic solvent mentioned in step 1 is any of the following systems: A: Choline chloride and zinc chloride are mixed at a mass ratio of 1:2; B: Choline chloride and zinc chloride are mixed at a mass ratio of 1:3; C: Choline chloride and zinc chloride monohydrate are mixed at a mass ratio of 1:2; D: Choline chloride and ferric chloride hexahydrate are mixed at a mass ratio of 1:2; E: Choline chloride and urea are mixed at a mass ratio of 1:2; F: Choline chloride and glycerol are mixed in a mass ratio of 1:2; G: Choline chloride and ethylene glycol are mixed at a mass ratio of 1:2; H: Choline chloride and lactic acid are mixed in a mass ratio of 1:2; I: Triethanolamine and lactic acid are mixed at a mass ratio of 1:

2.

4. The method for preparing a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network according to claim 1, characterized in that, The initiators mentioned in steps 1 and 3 include ultraviolet photoinitiators and thermal initiators. The photoinitiator is one or a combination of several of the following: 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 1-hydroxycyclohexylphenyl ketone (184), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), 2-methyl-2-(4-morpholino)-1-[4-(methylthio)phenyl]-1-propanone (907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (369), methyl benzoylformate (MBF), benzophenone (BP), aryl iodomonium salts, and mixed triaryl thiomonium salts. The thermal initiator is one or a combination of azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), and tert-butyl peroxide-2-ethylhexanoate.

5. The method for preparing a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network according to claim 1, characterized in that, The diamine mentioned in step 2 is one or a combination of cystamine, 1,6-hexanediamine, and ethylenediamine.

6. The method for preparing a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network according to claim 1, characterized in that, The ethylene glycol methyl ether acrylate and polyethylene glycol diacrylate mentioned in step 3 are the same as those in step 1; The hydroxyethyl acrylate includes hydroxyethyl acrylate and hydroxyethyl methacrylate; The lithium salt mentioned in step 3 is one or a combination of lithium bis(trifluoromethanesulfonyl)imide, lithium trifluoromethanesulfonyl-perfluorobutylsulfonylimide, lithium trifluoromethanesulfonyl-perfluoropropylsulfonylimide, lithium bis(fluorosulfonyl)imide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium difluoroborate oxalate, lithium difluorophosphate, lithium 4,5-dicyano-2-trifluoromethylimidazolium, and lithium chloride.

7. The method for preparing a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network according to claim 1, characterized in that, The ethylene glycol methyl ether acrylate, hydroxyethyl acrylate, polyethylene glycol diacrylate, lithium salt, and initiator mentioned in step 4 are the same as those in step 3.

8. The method for preparing a high mechanical strength ion-conducting elastomer based on a triple interpenetrating network according to claim 1, characterized in that, In steps 1, 3, and 4, the UV lamp used for photocuring has a wavelength of 350nm and an irradiation time of 2 to 30 minutes; when using thermal curing, the initiation temperature is 60 to 80°C.

9. A high mechanical strength ion-conducting elastomer based on a triple interpenetrating network, characterized in that, The high mechanical strength ion-conducting elastomer based on a triple interpenetrating network is prepared by the preparation method described in any one of claims 1-8.

10. An application of the high mechanical strength ion-conducting elastomer based on a triple interpenetrating network as described in claim 9, characterized in that, The specific application is in flexible electronic sensors.

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