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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—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
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- 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
本发明公开了一种高机械强度透明导电弹性体及其制备方法与应用，所述高机械强度透明导电弹性体由丙烯酸、四甲基氯化铵先制备得到澄清透明溶液，再进一步与植酸反应得到澄清透明溶液，再加入交联剂和光引发剂经紫外光固化得到高机械强度透明导电弹性体。所述制备方法简单快速，绿色环保，所制得的高机械强度透明导电弹性体同时兼具高机械强度和高拉伸性能，还具有较高的光学透过率和良好的自修复性能。所述高机械强度透明导电弹性能够作为柔性电子器件应用于应变传感器方面，具有巨大的市场应用价值。
The invention discloses a transparent conductive elastomer with high mechanical strength and a preparation method and application thereof. The transparent conductive elastomer with high mechanical strength is first prepared from acrylic acid and tetramethylammonium chloride to obtain a clear and transparent solution, and then further mixed with phytic acid. After the reaction, a clear and transparent solution is obtained, and then a cross-linking agent and a photoinitiator are added to obtain a transparent conductive elastomer with high mechanical strength through ultraviolet light curing. The preparation method is simple, fast, environmentally friendly, and the prepared transparent conductive elastomer with high mechanical strength has both high mechanical strength and high tensile performance, and also has high optical transmittance and good self-healing performance. The high-mechanical-strength transparent conductive elasticity can be applied to a strain sensor as a flexible electronic device, and has huge 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.
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