CN112745446A - High-mechanical-strength transparent conductive elastomer and preparation method and application thereof - Google Patents
High-mechanical-strength transparent conductive elastomer and preparation method and application thereof Download PDFInfo
- Publication number
- CN112745446A CN112745446A CN202011540620.6A CN202011540620A CN112745446A CN 112745446 A CN112745446 A CN 112745446A CN 202011540620 A CN202011540620 A CN 202011540620A CN 112745446 A CN112745446 A CN 112745446A
- Authority
- CN
- China
- Prior art keywords
- transparent conductive
- conductive elastomer
- mechanical strength
- high mechanical
- photoinitiator
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 85
- 239000000806 elastomer Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000002834 transmittance Methods 0.000 claims abstract description 11
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 21
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 21
- 229940068041 phytic acid Drugs 0.000 claims description 21
- 235000002949 phytic acid Nutrition 0.000 claims description 21
- 239000000467 phytic acid Substances 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- VSYDLUXFKAXBBY-UHFFFAOYSA-N C(C=1C(C(=O)O)=CC=CC1)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(COCCO)O Chemical compound C(C=1C(C(=O)O)=CC=CC1)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(COCCO)O VSYDLUXFKAXBBY-UHFFFAOYSA-N 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- -1 alkyl benzophenones Chemical class 0.000 claims description 3
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 3
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 14
- 239000013013 elastic material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 21
- 101150085511 PEDS1 gene Proteins 0.000 description 16
- 102100037592 Plasmanylethanolamine desaturase Human genes 0.000 description 16
- 229920003199 poly(diethylsiloxane) Polymers 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008859 change Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
Classifications
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-mechanical-strength transparent conductive elastomer, and a preparation method and application thereof. The preparation method is simple and quick, green and environment-friendly, and the prepared high-mechanical-strength transparent conductive elastomer has high mechanical strength and high tensile property, and also has high optical transmittance and good self-repairing performance. The high-mechanical-strength transparent conductive elastic material can be used as a flexible electronic device to be applied to the aspect of strain sensors, and has great market application value.
Description
Technical Field
The invention relates to the technical field of elastomer materials, in particular to a high-mechanical-strength transparent conductive elastomer and a preparation method and application thereof.
Background
Conductive Elastomers (CEs) have been widely used in various advanced flexible electronic devices such as sensors, flexible electrodes, wearable devices, and the like, and have promoted the development of the information society, making the human society increasingly intelligent. The CEs can adjust various properties of the final product, particularly mechanical properties (tensile strength, tensile strain, toughness and the like) by regulating and controlling the crosslinking density of the polymer network, so that the CEs with multiple functional characteristics and practical use value are designed and prepared. This advantage of CEs has generated a great research interest for researchers. However, most of the reported CEs today still do not meet the requirements of advanced electronic devices in terms of mechanical strength and strain at break, and generally, polymers with higher tensile stress have poorer tensile strain. Moreover, most of the reported CEs are opaque, colored or intrinsically non-conductive, and even many elastomers require complicated synthesis or preparation processes, which further limits the practical applications of CEs. In order to solve the existing problems, a simple and efficient 'all-in-one' chemical system is urgently needed from the source to obtain the elastomer with high mechanical strength, high stretchability, transparency and intrinsic conductivity. At the same time, the introduction of self-healing properties into these stretchable CEs can further reduce the impact of the CEs on the electrical and mechanical properties during deformation. Therefore, it is highly desirable to design and prepare CEs with excellent properties such as high mechanical strength, high tensile strength, high transparency and self-repairability
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides a preparation method of a transparent conductive elastomer with high mechanical strength, which is simple, quick, green and environment-friendly.
Another object of the present invention is to provide a high mechanical strength transparent conductive elastomer, which not only has high mechanical strength and high tensile property, but also has high optical transmittance and good self-repairing property.
Another object of the present invention is to provide the use of the high mechanical strength transparent conductive elastomer.
The technical scheme adopted by the invention is as follows:
a preparation method of a transparent conductive elastomer with high mechanical strength comprises the following steps:
(1) heating acrylic acid and tetramethylammonium chloride serving as a hydrogen bond donor and a hydrogen bond acceptor respectively at 60-90 ℃ until a uniform clear transparent solution 1 is formed, wherein the molar ratio of the acrylic acid to the tetramethylammonium chloride is 1: 2-1: 4;
(2) adding phytic acid into the clear transparent solution 1 obtained in the step (1), and heating at 60-90 ℃ until a uniform clear transparent solution 2 is formed again, wherein the dosage of the phytic acid is 5-15% of the total mass of the clear transparent solution 1;
(3) and (3) adding a crosslinking agent and a photoinitiator into the clear transparent solution 2 obtained in the step (2), wherein the addition amount of the crosslinking agent and the initiator is 0.1-5% of the molar mass of acrylic acid, uniformly stirring at room temperature to obtain a prepolymer solution, and polymerizing the prepolymer solution under UV irradiation to obtain the high-mechanical-strength transparent conductive elastomer.
The invention starts from the principle of 'integration' design, selects Acrylic Acid (AA) and tetramethylammonium chloride (TMAC) which can form high-density hydrogen bonds as a hydrogen bond donor and a hydrogen bond acceptor respectively, introduces Phytic Acid (PA) containing high-hydrogen bond density to form a TMAC-AA-PA type PDES system, and prepares transparent Conductive Elastomers (CEs) which simultaneously have high mechanical strength, high tensile property and self-repairing function after in-situ photopolymerization. The phytic acid contains 6 phosphorus hydroxyl groups, can form compact hydrogen bonds with COOH functional groups in a polymer network, and is dynamically broken and reconnected in the mechanical stretching process, so that the prepared CEs have excellent mechanical properties and self-repairing properties, and the contradiction between the tensile stress and the strain of the traditional elastomer material is overcome. The prepared CEs not only have high mechanical strength and ultrahigh tensile strain, but also have higher optical transmittance and good self-repairing performance (the product is a new product).
Preferably, the molar ratio of the acrylic acid to the tetramethylammonium chloride is 1: 2-1: 3.
Preferably, the dosage of the phytic acid is 8-12% of the total mass of the clear transparent solution 1.
Preferably, the cross-linking agent is one or more of tripropylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate phthalate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate.
Preferably, the photoinitiator is one or more of benzoin and derivatives photoinitiator, benzil photoinitiator, alkylbenzene photoinitiator and acyl phosphorus oxide photoinitiator. More specifically, the photoinitiator may be one or more of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 1173 (2-hydroxy-2-methyl-1-phenylpropanone), 184 (1-hydroxycyclohexylphenylketone), 2959 (2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone).
The high-mechanical-strength transparent conductive elastomer prepared by the preparation method.
Preferably, the high mechanical strength transparent conductive elastomer has a tensile stress of 2.12 to 66.61MPa, a tensile strain of 42 to 6169 percent and an ultraviolet transmittance in a visible light range of 92 to 94 percent.
Preferably, the conductivity of the high mechanical strength transparent conductive elastomer is 0.007S/m to 0.04S/m.
The high mechanical strength transparent conductive elastomer is applied to a strain sensor. The high mechanical strength transparent conductive elastomer of the invention can be assembled into a strain sensor for monitoring human activities.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention overcomes the contradiction between the tensile stress and the strain of the traditional elastomer material, and prepares the ultra-high-toughness transparent conductive elastomer with high mechanical strength and high tensile strain;
(2) the high-mechanical-strength transparent conductive elastomer also has high optical transmittance and good self-repairing performance;
(3) the preparation method of the high-mechanical-strength transparent conductive elastomer is simple, rapid, completely green and environment-friendly, and has great market application value.
Drawings
FIG. 1 is an infrared image of the elastomer obtained by direct curing of the components and TMAC-AA-PA type PDES.
FIG. 2 is an experimental graph showing that the transparent conductive elastomer prepared in example 2 can be lifted up by a weight 9500 times as much as its weight.
FIG. 3 is an optical photograph of the transparent elastomer prepared in example 2.
FIG. 4 is a graph of UV-optical transmittance of the transparent elastomer prepared in example 2.
Fig. 5 is an experimental diagram of the transparent conductive elastomer prepared in example 2 connected in series with a small LED bulb.
Fig. 6 is an ac impedance diagram of the transparent conductive elastomer prepared in examples 1 to 3.
Fig. 7 is a diagram of a self-repairability test experiment of the transparent conductive elastomer prepared in example 2.
FIG. 8 is a test chart of the application test of the transparent conductive elastomer prepared in example 2 as a strain sensor.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail with reference to specific embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The conductive polymerizable eutectic solvent with the self-repairing function is researched before the subject group, the cross-linking agent can be one or more of polyethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate phthalate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate, and the photoinitiator can be one or more of benzoin and derivative photoinitiators, benzil photoinitiators, alkylbenzene photoinitiators and acylphosphorus oxide photoinitiators. For those skilled in the art, based on the experimental results of one of the cross-linking agents and the photo-initiator applied to the preparation of the high mechanical strength transparent conductive elastomer, it can be speculated that the use of the other related cross-linking agent and the photo-initiator necessarily has similar performance, so the patent does not perform experiments on all the photo-initiators and the cross-linking agents to be exhaustive.
The following examples are all common commercial products as starting materials unless otherwise specified.
The acrylic acid used in the following examples was used before use
Drying the molecular sieve, and drying the tetramethylammonium chloride at 60 ℃ for 2 hours in vacuum before use.
Examples 1 to 3
A transparent conductive elastomer with high mechanical strength is prepared by the following steps:
(1) preparation of TMAC-AA type PDES: tetramethylammonium chloride and acrylic acid were mixed in a molar ratio of 1:2, and the mixture was heated in a closed flask at 65 ℃ until a homogeneous clear transparent solution 1, noted as TMAC-AA type PDES, was formed, which was kept in a vacuum desiccator with silica gel for further use.
(2) Preparation of TMAC-AA-PA type PDES: TMAC-AA type PDES and PA were mixed in a mass ratio of 1: 5% (example 1), 1: 10% (example 2), 1: 15% (example 3), the mixture was heated in a closed flask at 65 ℃ until a homogeneous clear transparent solution 2 was formed, designated as TMAC-AA-PA type PDES, which was kept in a vacuum desiccator with silica gel and was ready for further use.
(3) Photopolymerization: adding a cross-linking agent PEG (200) DA and a photoinitiator 2959 into TMAC-AA-PA type PDES, wherein the addition amount of the cross-linking agent and the initiator is 0.1 percent of the molar mass of the acrylic monomer, and stirring uniformly at room temperature to obtain a prepolymer solution of a mixed liquid. A certain amount of prepolymer solution is placed in a vessel or a mold, and then a UV light source (the light intensity is 20mW cm-2) The polymerization can be completed after the irradiation for 2 minutes, and the transparent conductive elastomer with high mechanical strength is obtained.
Example 4
A high mechanical strength transparent conductive elastomer was prepared in substantially the same manner as in example 1 except that the mass ratio of TMAC-AA type PDES to PA in this example was 1: 8%.
Example 5
A high mechanical strength transparent conductive elastomer was prepared in substantially the same manner as in example 1 except that the mass ratio of TMAC-AA type PDES to PA in this example was 1: 12%.
Example 6
A high mechanical strength transparent conductive elastomer was prepared in substantially the same manner as in example 2 except that in example 4, the molar ratio of tetramethylammonium chloride to acrylic acid was 1:4, respectively.
Example 7
A high mechanical strength transparent conductive elastomer was prepared in substantially the same manner as in example 2 except that in example 4, the molar ratio of tetramethylammonium chloride to acrylic acid was 1:3, respectively.
Example 8
A transparent conductive elastomer with high mechanical strength was prepared in substantially the same manner as in example 2 except that in example 5, the polyethylene glycol diacrylate in example 2 was replaced with an equimolar amount of tripropylene glycol diacrylate.
Example 9
A high mechanical strength transparent conductive elastomer was prepared in substantially the same manner as in example 2 except that in example 6, the crosslinking agent was added in an amount of 5% by mole based on the acrylic monomer.
Performance testing
(1) And (3) infrared testing: the method adopts a VERTEX 70 Fourier transform infrared spectrometer for testing, and the wave number scanning range is 500-4000cm-1Setting resolution to 4cm-1. The environmental conditions tested were room temperature 25 deg.C and humidity 30% -35%. The test samples included TMAC-AA type PDES, Acrylic Acid (AA), tetramethylammonium chloride (TMAC), Phytic Acid (PA) and Elastomers (Elastomers) obtained after direct curing of TMAC-AA-PA type PDES.
(2) And (3) ultraviolet testing: cutting Conductive Elastomer (CEs) sample size of 1 × 1cm2And testing by adopting an ultraviolet visible spectrophotometer (S3100) to obtain the optical transmittance of the CEs under the test conditions of room temperature 25 ℃ and humidity of 30-35%.
(3) And (3) testing mechanical properties: cutting the CEs to 2 × 5 × 0.1cm3And testing the mechanical properties of the CEs by using an INSTRON 5565 type tensile compression material testing machine under the test conditions of room temperature 25 ℃ and humidity of 30-35%.
(4) And (3) testing electrical properties: the CEs samples were cut to a size of 1X 2X 0.1cm3And connecting a copper sheet with a lead, and testing by adopting a PARSTAT 2273 type electrochemical workstation to obtain the electrical properties of the CEs. The current of the electrochemical workstation is 200mA, and the frequency range is 0.01-105Hz. The test conditions are that the room temperature is 25 ℃ and the humidity is 30-35%.
(5) Metallographic microscope: and (3) placing the CEs samples before and after the repair under an OLYMPUS BX63 type metallographic microscope, and taking an optical photo of the self-repair process.
(6) Optical picture shooting: optical photographs of the CEs were taken using a Nikon Digital Sight DS-Fil camera.
The infrared spectrum of TMAC-AA-PA type PDES prepared in example 2 is shown in the left part of FIG. 1, and is compared with the infrared spectra of Acrylic Acid (AA), tetramethylammonium chloride (TMAC) and Phytic Acid (PA), and the infrared spectrum of TMAC-AA-PA type PDES and the elastomer obtained by curing the same is shown in the right part of FIG. 1, and it is understood from the graph that 3343cm is obtained after curing-Peak (-OH, -NH) at 1 to 3373cm low-1Transferring while 1621cm-1The peak (C ═ C) at (a) was largely disappeared, indicating efficient polymerization of the double bond. These results show that the PDESs arePrepared by a rapid photopolymerization process from covalent bonds and hydrogen bonds.
The results of the mechanical property tests of examples 1 to 9 are shown in table 1.
TABLE 1
| Test items | Tensile stress | Tensile strain |
| Example 1 | 66.61MPa | 42％ |
| Example 2 | 31.21MPa | 3645％ |
| Example 3 | 4.39MPa | 6169％ |
| Example 4 | 54.36MPa | 414.26％ |
| Example 5 | 15.52MPa | 3570％ |
| Example 6 | 2.12MPa | 1095％ |
| Example 7 | 16.39MPa | 1753％ |
| Example 8 | 29.51MPa | 3010％ |
| Example 9 | 41.08MPa | 950％ |
As can be seen from Table 1, the transparent conductive elastomer prepared by the present invention has high mechanical strength and tensile strain, and the tensile stress and strain can reach 31.21MPa and 3645%. As can be seen from the data of examples 1 to 3, the tensile strain of the conductive elastomer gradually increases as the PA content increases. The best balance between tensile stress and strain is achieved at the same time when the PA content is 10%. FIG. 2 is a graph showing an experiment that the transparent conductive elastomer prepared in example 2 can lift a heavy object 9500 times its weight.
The conductive elastomer prepared by the present invention also has high transparency and very transparent appearance, and an optical photograph of the transparent elastomer prepared in example 2 is shown in fig. 3. The conductive elastomer disclosed by the invention shows light transmittance of more than 92% in a visible light range, and shows that the prepared CEs have excellent optical transparency and great potential in application to optical and electronic devices. Fig. 4 shows the result of the optical transmittance test of the conductive elastomer according to example 2 using an S3100 type uv-vis spectrophotometer, which showed 94% light transmittance.
The TMAC not only provides hydrogen bonds, but also provides conductive ions for the conductive elastomer in the PDES system, and endows the conductive elastomer with intrinsic ionic conductivity, and the transparent conductive elastomer prepared in the embodiments 1 to 9 of the invention can be connected with the LED small bulb in series to enable the small bulb to continuously emit light, which shows that the transparent conductive elastomer prepared in the invention has good conductivity. Fig. 5 is an experimental diagram of the transparent conductive elastomer prepared in example 2 connected in series with a small LED bulb.
The transparent conductive elastomer prepared by the present invention also has better electrochemical properties, for example, fig. 6 is an ac impedance diagram of the transparent conductive elastomers prepared in examples 1 to 3. As the PA content increased, the conductivity of the conductive elastomer increased from 0.007S/m to 0.04S/m. As can be seen, the increase in conductivity may be due to the polymer network swelling more in the PA as the PA content increases, thereby providing more channels for ions in the TMAC.
The transparent conductive elastomer prepared by the invention also has excellent self-repairing performance, and when a series experiment of the transparent conductive elastomer and the LED small bulb is carried out, the transparent conductive elastomer prepared in the embodiments 1 to 9 of the invention is cut into two halves, and then the two halves are contacted with each other, and then the conductivity can be automatically recovered. Fig. 7-a is an experimental graph of the transparent conductive elastomer prepared in example 2 and the LED small bulb connected in series, in the experiment, an optical microscope is used to study and record the self-repairing performance of the CEs after cutting, and fig. 7-d is a test graph of the self-repairing performance, as can be seen from the graph, as the repairing time is prolonged, the dynamic hydrogen bonds attract the polymer chains to diffuse at the fracture interface and participate in new cross-linking, so that the mark after cutting disappears after 24 h. As shown in FIG. 7-b, which is a graph for testing the electrical properties of the conductive elastomer in the off-contact state, it can be seen from FIG. 7-b that the conductive elastomer can recover 99% of the initial resistance value within 0.26s, so that the LED small bulb can continuously emit light (as shown in FIG. 7-c), indicating that the LED small bulb has excellent electrical self-repairing properties and stable electrical properties.
In order to further illustrate the possibility of practical application of the prepared high-mechanical-strength transparent conductive elastomer in flexible electronic devices and the excellent mechanical properties and load-bearing capacity of the conductive elastomer, experiments are also carried out to construct the high-mechanical-strength transparent conductive elastomer into a strain sensor for detecting human body movement. As shown in fig. 8(a), the strain sensor assembled in the experiment includes the high mechanical strength transparent Conductive Elastomer (CE) of example 2, a 3M tape (3M tape), and a Metal wire (Metal wire). As shown in fig. 8(b), the assembled sensor accurately records the resistance changes of different movements of the volunteer, and these results show that the transparent conductive elastomer can accurately reflect different movement movements of the human body through the amplitude and frequency of the electric signal. In addition, as shown in the inset of fig. 8(c), the transparent conductive elastomer was also integrated into the series circuit with the LED small bulb and cyclically stretched (strain 0-300%) during the experiment. As can be seen from fig. 8(c), the electrical stability of CEs was further confirmed by the fact that the resistance change rate of CEs was almost the same in the same tensile strain and the LED small bulb continued to emit light. As shown in fig. 8(d-e), the transparent conductive elastomer was also fixed at the joints of the index finger and the elbow in the experiment, and the change of the electrical signals of the joints at different bending angles was observed and recorded. As can be seen from fig. 8(d-e), the change of the electrical signal is uniform and consistent under the same bending angle, further demonstrating the electrical stability and good repeatability of CEs, indicating that it has great application prospect in stretchable electronic devices.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.
Claims (9)
1. A preparation method of a transparent conductive elastomer with high mechanical strength is characterized by comprising the following steps:
(1) heating acrylic acid and tetramethylammonium chloride serving as a hydrogen bond donor and a hydrogen bond acceptor respectively at 60-90 ℃ until a uniform clear transparent solution 1 is formed, wherein the molar ratio of the acrylic acid to the tetramethylammonium chloride is 1: 2-1: 4;
(2) adding phytic acid into the clear transparent solution 1 obtained in the step (1), and heating at 60-90 ℃ until a uniform clear transparent solution 2 is formed again, wherein the dosage of the phytic acid is 5-15% of the total mass of the clear transparent solution 1;
(3) and (3) adding a crosslinking agent and a photoinitiator into the clear transparent solution 2 obtained in the step (2), wherein the addition amount of the crosslinking agent and the initiator is 0.1-5% of the molar mass of acrylic acid, uniformly stirring at room temperature to obtain a prepolymer solution, and polymerizing the prepolymer solution under UV irradiation to obtain the high-mechanical-strength transparent conductive elastomer.
2. The method for preparing a transparent conductive elastomer with high mechanical strength according to claim 1, wherein the molar ratio of acrylic acid to tetramethylammonium chloride is 1:2 to 1: 3.
3. The method for preparing a transparent conductive elastomer with high mechanical strength as claimed in claim 1, wherein the phytic acid is used in an amount of 8 to 12% by mass of the total mass of the transparent clear solution 1.
4. The method of claim 1, wherein the crosslinking agent is one or more of tripropylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate phthalate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.
5. The method for preparing the high-mechanical-strength transparent conductive elastomer as claimed in claim 1, wherein the photoinitiator is one or more of benzoin and derivatives photoinitiator, benzil photoinitiator, alkyl benzophenones photoinitiator, and acyl phosphorous oxide photoinitiator.
6. The transparent conductive elastomer with high mechanical strength prepared by the preparation method of any one of claims 1 to 5.
7. The high mechanical strength transparent conductive elastomer according to claim 6, wherein the tensile stress of the high mechanical strength transparent conductive elastomer is 2.12MPa to 66.61MPa, the tensile strain is 42% to 6169%, and the ultraviolet transmittance in the visible light range is 92% to 94%.
8. The high mechanical strength transparent conductive elastomer according to claim 6, wherein the conductivity of the high mechanical strength transparent conductive elastomer is 0.007S/m to 0.04S/m.
9. Use of a high mechanical strength transparent conductive elastomer according to any one of claims 6 to 8 in a strain sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011540620.6A CN112745446B (en) | 2020-12-23 | 2020-12-23 | High-mechanical-strength transparent conductive elastomer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011540620.6A CN112745446B (en) | 2020-12-23 | 2020-12-23 | High-mechanical-strength transparent conductive elastomer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112745446A true CN112745446A (en) | 2021-05-04 |
| CN112745446B CN112745446B (en) | 2022-02-18 |
Family
ID=75647342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011540620.6A Active CN112745446B (en) | 2020-12-23 | 2020-12-23 | High-mechanical-strength transparent conductive elastomer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112745446B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160122676A1 (en) * | 2014-11-03 | 2016-05-05 | Exxonmobil Research And Engineering Company | Low transition temperature mixtures or deep eutectic solvents and processes for preparation thereof |
| CN107177024A (en) * | 2017-05-23 | 2017-09-19 | 广州纽楷美新材料科技有限公司 | Application of the polymerizable eutectic solvent in electrically conducting transparent elastomer is prepared |
| CN110054721A (en) * | 2019-05-10 | 2019-07-26 | 华南理工大学 | Application and ionic gel and preparation method of the eutectic solvent in ionic gel |
| CN110157013A (en) * | 2019-05-30 | 2019-08-23 | 福州大学 | A kind of preparation method of high stretch polyaniline compliant conductive hydrogel |
| CN110982093A (en) * | 2019-12-25 | 2020-04-10 | 湖北理工学院 | Method for preparing quick-response temperature-sensitive hydrogel by adopting room-temperature eutectic solvent liquid front-end polymerization |
| CN111196866A (en) * | 2020-01-02 | 2020-05-26 | 华南理工大学 | Preparation method of transparent conductive small ball, transparent conductive small ball and application |
| CN111253520A (en) * | 2018-12-03 | 2020-06-09 | 华南理工大学 | Polymerizable eutectic solvent for self-repairing material, conductive elastomer and preparation method |
-
2020
- 2020-12-23 CN CN202011540620.6A patent/CN112745446B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160122676A1 (en) * | 2014-11-03 | 2016-05-05 | Exxonmobil Research And Engineering Company | Low transition temperature mixtures or deep eutectic solvents and processes for preparation thereof |
| CN107177024A (en) * | 2017-05-23 | 2017-09-19 | 广州纽楷美新材料科技有限公司 | Application of the polymerizable eutectic solvent in electrically conducting transparent elastomer is prepared |
| CN111253520A (en) * | 2018-12-03 | 2020-06-09 | 华南理工大学 | Polymerizable eutectic solvent for self-repairing material, conductive elastomer and preparation method |
| CN110054721A (en) * | 2019-05-10 | 2019-07-26 | 华南理工大学 | Application and ionic gel and preparation method of the eutectic solvent in ionic gel |
| CN110157013A (en) * | 2019-05-30 | 2019-08-23 | 福州大学 | A kind of preparation method of high stretch polyaniline compliant conductive hydrogel |
| CN110982093A (en) * | 2019-12-25 | 2020-04-10 | 湖北理工学院 | Method for preparing quick-response temperature-sensitive hydrogel by adopting room-temperature eutectic solvent liquid front-end polymerization |
| CN111196866A (en) * | 2020-01-02 | 2020-05-26 | 华南理工大学 | Preparation method of transparent conductive small ball, transparent conductive small ball and application |
Non-Patent Citations (2)
| Title |
|---|
| REN"AI LI等: ""Highly transparent, self-healing conductive elastomers enabled by synergistic hydrogen bonding interactions"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| TAO WANG等: ""A Self-Healable, Highly Stretchable, and Solution Processable conductive Polymer Composite for Ultrasensitive Strain and Pressure Sensing"", 《ADV. FUNCT. MATER. 》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112745446B (en) | 2022-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Integration of hydrogen bonding interaction and Schiff-base chemistry toward self-healing, anti-freezing, and conductive elastomer | |
| Chen et al. | Patternable transparent and conductive elastomers towards flexible tactile/strain sensors | |
| Fan et al. | Highly transparent, self-healing conductive elastomers enabled by synergistic hydrogen bonding interactions | |
| CN111253520B (en) | Polymerizable eutectic solvent for self-repairing material, conductive elastomer and preparation method | |
| CN112708014B (en) | Recyclable self-repairing transparent conductive elastomer and preparation method and application thereof | |
| Yu et al. | Carbon Dots‐Based Ultrastretchable and Conductive Hydrogels for High‐Performance Tactile Sensors and Self‐Powered Electronic Skin | |
| Zhang et al. | Peptidoglycan-inspired autonomous ultrafast self-healing bio-friendly elastomers for bio-integrated electronics | |
| Zhang et al. | Self-healing, mechanically robust, 3D printable ionogel for highly sensitive and long-term reliable ionotronics | |
| CN109764980B (en) | Preparation method of double reversible bond room temperature self-healing silicon rubber pressure sensor | |
| Zhang et al. | Double network hydrogel sensors with high sensitivity in large strain range | |
| Sun et al. | Ultra-stretchable, self-adhesive, transparent, and ionic conductive organohydrogel for flexible sensor | |
| CN110595347A (en) | Low-Young modulus hydrogel flexible strain sensor | |
| Peng et al. | A photoresponsive azopyridine-based supramolecular elastomer for self-healing strain sensors | |
| CN113621100A (en) | Polymerizable eutectic solvent, dry-type ion conductor prepared from polymerizable eutectic solvent and preparation method of dry-type ion conductor | |
| CN116496436B (en) | Preparation method and application of multi-hydrogen bond network-based self-repairing high-transparency conductive elastomer | |
| Yang et al. | Deep Eutectic Solvent‐Based Ultra‐Stretchable, Anti‐Freezing, and Ambient‐Stable Supramolecular Ionogel for Wearable Sensor | |
| Yao et al. | Granular ionogel particle inks for 3D printed tough and stretchable ionotronics | |
| Wang et al. | Conductive double-crosslinked network hydrogel with superior stretchability and self-healing ability | |
| CN115651228A (en) | Preparation method and application of cellulose-based ionic gel | |
| CN112745446B (en) | High-mechanical-strength transparent conductive elastomer and preparation method and application thereof | |
| CN113185715A (en) | Self-healing conductive polyvinyl alcohol-based hydrogel and preparation method and application thereof | |
| Zhang et al. | Ultrastretchable and adhesive MXene-based hydrogel for high-performance strain sensing and self-powered application | |
| CN108753182A (en) | A kind of OCA optical cements haveing excellent performance, optical adhesive tape and preparation method thereof | |
| Liu et al. | Preparation of MPASP‐PAA/Fe3+ Composite Conductive Hydrogel with Physical and Chemical Double Crosslinking Structure and Its Application in Flexible Strain Sensors | |
| CN116396448B (en) | Polymerizable deep eutectic gel and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |