TWI784598B - Self-healing copolymerized polymer material and manufacturing method thereof as well as light-emitting material, white led backlight display, conductive electrode material, organic light-emitting diode, and flexible light-emitting electronic device containing the same - Google Patents

Abstract

The instant invention provides a self-healing copolymerized polymer material and a manufacturing method thereof as well as a light-emitting material, a white led backlight display, a conductive electrode material, an organic light-emitting diode, and a flexible light-emitting electronic device containing the same. The self-healing copolymerized polymer material is PDMS-MDI _x-TFB _1-x, wherein x is 0.1-0.9. By adjusting the ratio of MDI and TFB, the synthesized self-healing copolymerized polymer material has excellent performance. A higher ratio of TFB has better self-healing efficiency, and can be self-healing under various circumstances.

Description

Self-healing copolymerized polymer material and its manufacturing method, as well as light-emitting material containing it, white LED backlight display, conductive electrode material, organic light-emitting diode and flexible light-emitting electronic components

The invention provides a self-healing copolymerized polymer material and its manufacturing method, as well as a luminescent material containing the same, a white LED backlight display, a conductive electrode material, an organic light-emitting diode and a flexible light-emitting electronic component, especially the copolymerized high polymer material. The molecular material is a copolymerized polymer of polydimethylsiloxane (PDMS), diphenylmethane diisocyanate (MDI) and 1,3,5-benzenetricarbaldehyde (TFB).

In the field of material science, polymers occupy a very important position. Polymers are also the most widely used materials by humans. The use of polymer materials can be traced back to the use of natural polymer materials such as bark and straw in primitive times. After the 20th century, polymer materials were produced by artificial synthesis. In 1941, the British Whinfield and Dickson first synthesized polyethylene terephthalate (PET), and then the famous American DuPont Company produced Dacron fiber, Terylene, Terlenka and Terlenka. Man-made fibers such as Tetoron, through which people began to use a large number of PET fibers to make clothes, and widely used synthetic polymer materials.

Since many materials are exposed to the wind and the sun for many years, they will gradually cause problems such as material aging and damage. Therefore, scientists began to think whether it is possible to transfer the self-healing properties of human beings to polymer materials, so as to avoid frequent replacement of materials and prolong the life of materials. service life.

The construction industry first started to use self-healing materials. They embedded the healing agent that can produce cross-linking reactions into the cement in the form of microcells. When the microcells are destroyed, they can release the healing agent to generate cross-linking and self-healing. . However, since the embedded microcells can only perform one-time self-repair, reversible dynamic chemical bonds are used for self-repair, such as: Diels-Alder reaction, thiol reaction and reversible imine bond, etc. .

In addition to the above-mentioned covalent chemical bonds, many scientists also use various forces for self-healing, such as hydrogen bond forces, electrostatic forces, and hydrophobic forces. Self-healing polymer materials have a self-healing function similar to that of human skin. Many people have begun to make self-healing polymers into artificial electronic skin (E-skin). Currently, this electronic skin is mostly used in robotic arms. In the future, artificial Electronic skin applied to robots.

However, the self-healing polymers in the past need to be heated to trigger their self-healing mechanism, and the reaction temperature to start the self-healing reaction usually needs to exceed 100°C. Because the temperature is too high, it is inconvenient to use and easy to cause danger. Therefore, , In order to solve the above problems, the present inventors started to improve the repair mechanism of self-healing polymers.

The inventors have developed a polymer material that can be self-repaired at room temperature, and the self-repairable copolymerized polymer material of the present invention uses a dual self-repair mechanism to improve self-repair efficiency and maintain low temperature (-10 ℃) can also perform self-healing.

The self-healing copolymer polymer material of the present invention is: polydimethylsiloxane (PDMS), diphenylmethane diisocyanate (MDI) and 1,3,5-benzenetricarbaldehyde (TFB) The copolymerized polymer PDMS-MDI _x -TFB _1-x , wherein X is 0.1~0.9.

Further, in the copolymerized polymer material, X is 0.4.

Further, the copolymerized polymer material has self-healing functional groups with hydrogen bonds and imine bonds.

Further, the copolymerized polymer material has a PDI (Polymer dispersion index, polymer dispersion index) of 1.4-1.7.

Further, the glass transition temperature (T _g ) of the copolymerized polymer material is -110 to -130°C.

The present invention also provides a method for self-healing copolymerized polymer materials, comprising: (1) bis(3-aminopropyl)-terminated poly(dimethylsiloxane) ), NH ₂ -PDMS-NH ₂ ) and diphenylmethane diisocyanate (4,4-methylenebis (phenyl isocyanate), MDI) polymerization to obtain PDS-MDI; and (2) the PDS-MDI and 1,3, 5-Benzenetriformaldehyde (1,3,5-triformylbenzene, TFB) was polymerized to obtain PDMS-MDI-TFB.

In addition/alternatively, the present invention provides a luminescent material comprising the copolymerized polymer material mixed with perovskite quantum dots.

The present invention also provides a white LED backlight display, which includes a blue LED chip and two layers of luminescent materials superimposed on it, wherein the two layers of luminescent materials are respectively copolymerized polymer materials mixed with green perovskite quantum dots , and the copolymerized polymer material mixed with red perovskite quantum dots.

The present invention also provides a conductive electrode material, which comprises the above-mentioned copolymerized polymer material mixed with nano metal wires.

Further, the conductive electrode material as described above, wherein the nanometer metal wires are metallic silver wires.

The present invention also provides an organic light-emitting diode, which includes a light-emitting layer and the above-mentioned conductive electrode material as electrodes.

On the other hand, the present invention also provides a flexible light-emitting electronic component, which includes the above-mentioned organic light-emitting diode, and an insulating film is used to block the light-emitting layer and the electrode, and the insulating film does not completely cover the light-emitting layer, When bending the flexible light-emitting electronic element, the light-emitting layer and the electrode are in contact.

Compared with the conventional technology, the copolymerized polymer material of the present invention can self-heal at room temperature, and it uses a dual self-healing mechanism to improve self-healing efficiency, and can also perform self-healing at low temperature (-10°C) , greatly increasing the commercial utilization of this polymer material.

The present invention is described below so that those skilled in the art can easily understand the essential technology of this invention, and as long as it does not violate the spirit and scope, this invention can be changed and modified in various ways to adapt to different uses and situations. In this way, other embodiments are also included in the scope of the patent application.

The detailed description and technical contents of the present invention are described as follows with respect to the accompanying drawings. Furthermore, for the convenience of explanation, the proportions of the drawings in the present invention are not necessarily drawn according to the actual scale. These drawings and their proportions are not intended to limit the scope of the present invention, and are described here first.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The following terms used throughout this application shall have the following meanings.

The invention provides a self-healing copolymerized polymer material, which is: PDMS-MDI _x -TFB _1-x , wherein _X is 0.1-0.9. Moreover, the present invention also relates to a method for manufacturing the aforementioned self-healing copolymerized polymer material, comprising: (1) bis(3-aminopropyl)-terminated polydimethylsilane (bis(3 -aminopropyl)-terminated poly(dimethylsiloxane), NH ₂ -PDMS-NH ₂ ) and diphenylmethane diisocyanate (4,4-methylenebis(phenyl isocyanate), MDI) are polymerized to obtain PDS-MDI; and (2) the PDS-MDI is polymerized with 1,3,5-triformylbenzene (TFB) to obtain PDMS-MDI-TFB.

X in the aforementioned PDMS-MDI _x -TFB _{1-x is} 0.1-0.9, for example: 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9. In a preferred embodiment, the _X is 0.4.

The "self-healing" mechanism described in this article is mainly divided into embedded type and essential type. However, due to the great disadvantage of embedded type self-healing, when the embedded healing agent is released, self-repairing cannot be performed any more, so this paper The self-healing mechanism of the invention is based on the essential type of self-healing. Bonds that can be destroyed and then recombined must be placed in the design of the polymer, and reversible chemical reactions must be introduced for self-healing. Essential self-healing is a reversible phenomenon of chemical bond destruction and generation, which is divided into reversible covalent bonds and non-covalent bonds. In a preferred embodiment, the PDMS-MDI _x -TFB _1-x of the present invention uses non-covalent bonds Hydrogen bonds and imine bonds of reversible covalent bonds contain two self-healing functional groups at the same time.

The "self-healing functional group" mentioned in this article means that the copolymerized polymer material uses a functional group capable of hydrogen bonding and a reversible covalent bond type utilizing a dynamic chemical bond mechanism as the main elements for self-healing. Hydrogen bonds usually occur on two atoms with high electronegativity (N, O, F). The hydrogen atoms are first covalently bonded to one atom, and then bonded to the other atom by hydrogen bonding force. Due to the covalent The bonded atom has a strong negative charge, which attracts the electron cloud on the hydrogen atom, so the hydrogen atom has a strong positive charge, and is attracted by the negative charge on the other atom, thereby generating a hydrogen bond force. In this hydrogen-bonded self-healing polymer, functional groups with hydrogen bonds are often generated by condensation polymerization, such as amide bonds formed by carboxylic acid groups and amine groups or amide bonds formed by isocyanate groups and amine groups. Urea group (urea). A typical reversible covalent bond is the Diels-Alder reaction, which uses the cycloaddition reaction of conjugated diene and olefin to form cyclohexene. Due to the reversibility of this reaction, it achieves the effect of self-healing. The disulfide bond is also a reversible reaction. When the disulfide bond is decomposed, it is reduced to a thiol, and then re-bonded to form a disulfide bond to generate self-repair.

Hydrogen-bonded self-healing requires the use of increased temperature to break hydrogen bonds. When the temperature is removed, the urea groups that generate hydrogen bonds rebond to produce self-healing. In the past, reversible covalent self-healing also required heating to generate a reaction, but the reversible imine bond of the PDMS-MDI _x -TFB _1-x of the present invention can undergo a reversible reaction at room temperature, so when the unbonded amine group When in contact with an aldehyde group, a reversible imine bond can be generated for self-healing. The copolymerized polymer material of the present invention utilizes multiple mechanisms to effectively improve the efficiency of self-healing.

In a preferred embodiment, the copolymerized polymer material has a PDI (Polymer dispersion index) of 1.4-1.7, for example: 1.4, 1.5, 1.6 or 1.7. When the PDI value is too large, it means that the molecular weight distribution is too large and the length of the molecular chain is uneven. This phenomenon will cause the self-repairing group to be separated and difficult to recombine, resulting in a decline in the self-repairing effect. When the PDI value is greater than 2, it will show poor self-repair. Repair effect.

In a preferred embodiment, the copolymerized polymer material has a glass transition temperature of -110 to -130°C, for example: -110 to -130°C, -110 to -125°C, -110 to -120°C, - 110 to -115°C, -115 to -130°C, -115 to -125°C, -115 to -120°C, -120 to -130°C, -120 to -125°C, or -125 to -130°C. The "glass transition temperature (T _g )" mentioned in this article refers to the temperature range when the polymer material changes from the glassy state to the rubber state, which is called the glass transition temperature. When the polymer temperature is higher than the glass transition temperature, it will change from a hard and brittle glass state to a soft and tough rubber state. E”/E’ is the damping curve tanδ as the T _g point of the polymer material; among them, the storage modulus (Storage modulus, E’) is measured based on the elastic properties of the material and the resistance of external factors The parameters obtained, the loss modulus (Loss modulus, E") is a parameter measured based on the viscous properties of the material and the consumption of external factors. When the T _g point is lower, it means that the polymer chain is easier to move, making it easier for the functional groups capable of self-repair to touch and achieve the effect of self-repair. The glass transition temperature of polymers can be measured using a dynamic thermal analyzer (DMA).

Another aspect of the present invention provides a variety of applications of self-healing copolymerized polymer materials, such as luminescent materials containing the copolymerized polymer materials, white LED backlight displays, conductive electrode materials, organic light-emitting diodes, flexible light-emitting electronic components Wait.

In a preferred embodiment, the luminescent material provided by the present invention comprises the aforementioned copolymerized polymer material mixed with perovskite quantum dots. In a preferred embodiment, the white light LED backlight display provided by the present invention comprises a blue light LED chip, and two layers of luminescent materials as mentioned above are stacked respectively on it, wherein the two layers of luminescent materials are respectively copolymerized The polymer material is mixed with green perovskite quantum dots, and the copolymerized polymer material is mixed with red perovskite quantum dots.

The "Perovskite" material mentioned in this article refers to a class of crystalline ceramic oxides with a body-centered cubic structure. The molecular formula of this type of crystal is generally represented by ABX ₃ , where A and B are cations, and Most of X are anions such as oxygen or halogen, wherein A is for example: CH ₃ NH ₃ ⁺ , cesium cation (Cs ⁺ ), CH ₃ NH ₃ ⁺ or Formamidinium (HC(NH ₂ ) ²⁺ ), etc., but the present invention is not limited to and so on; where B is for example: Pb ²⁺ , Ge ²⁺ , Sn ²⁺ , etc., but the present invention is not limited thereto; where X is for example: oxygen ion, chloride ion (Cl ^- ), bromide ion (Br ^- ), iodine Ions (I ^- ), etc., or oxygen groups or halogen groups containing them, but the present invention is not limited thereto. Perovskite materials can achieve 2D, 1D, and 0D structures in different structural dimensions from the fine control of the octahedral structure, while the perovskite quantum dots are quasi-zero nanomaterials, and the three dimensions are all below 100 nanometers. The lattice size is 2-20 nanometers. Since the perovskite quantum dot has wavelength tunability, high quantum efficiency and narrow half-width, it is the preferred light-emitting material of the present invention. In addition, luminescent materials of different colors can be obtained by adjusting the halogen composition in the perovskite.

In this paper, the contact angle meter is used to measure the contact angle between the substance and water droplets, and the affinity and hydrophobicity of the substance can be judged by the contact angle. These data can be used to improve the compatibility of the surface of the substance. The most common measurement method for contact angle is the sessile drop method (Sessile Drop), which performs drop titration on a solid plane. The principle is based on the contact angle calculation theory Young’s equation. The larger the contact angle between a substance and a water droplet, the higher the hydrophobicity; the smaller the contact angle between a substance and a water droplet, the higher the hydrophilicity. When the contact angle is less than 10 degrees, it is called superhydrophilic; when the contact angle is between 10 and 90 degrees, it is hydrophilic; between 90 and 120 degrees, it is hydrophobic; and if it is greater than 120 degrees, it is called superhydrophobicity. In a preferred embodiment, the film made of the luminescent material of the present invention is hydrophobic. In a preferred embodiment, the film made of the luminescent material of the present invention has a contact angle of 90°~120°, for example: 90°~120°, 90°~115°, 90°~110°, 90°~ 105°, 90°~100°, 90°~95°, 95°~120°, 95°~115°, 95°~110°, 95°~105°, 95°~100°, 100°~120° , 100°~115°, 100°~110°, 100°~105°, 105°~120°, 105°~115°, 105°~110°, 110°~120° or 110°~115°.

In a preferred embodiment, the conductive electrode material provided by the present invention comprises the aforementioned copolymerized polymer material mixed with nano metal wires. In a preferred embodiment, the organic light-emitting diode provided by the present invention includes a light-emitting layer and the above-mentioned conductive electrode material as electrodes. In addition, the flexible light-emitting electronic component provided by the present invention includes the above-mentioned organic light-emitting diode, and an insulating film is used to block the light-emitting layer and the electrode, and the insulating film does not completely cover the light-emitting layer, so that When the flexible light-emitting electronic element is bent, the light-emitting layer and the electrode are in contact.

The "nanometal wire" mentioned in this article refers to a one-dimensional structure with a diameter of nanometers (10 ^-9 meters) and no limitation in length. There are many types of metal nanowires. Among them, nanowires such as gold nanoparticles, silver nanoparticles, and copper nanoparticles not only have excellent electrical conductivity, but also have excellent light transmission and flex resistance under the nanoscale size effect. Therefore, it is considered to be the most suitable material to replace the traditional indium tin oxide (ITO) transparent electrode, providing the best possibility for the realization of flexible, bendable LED display, touch screen and other applications; in addition, it can also be used for thin films Solar battery. Nano-copper wires and nano-silver wires have large aspect ratio characteristics, so that they also have considerable advantages in conductive adhesives and thermal conductive adhesives; others such as nano-gold wires with large aspect ratios, nano-tellurium wires or various Nano metal oxides such as titanium oxide nanowires, molybdenum oxide nanowires, tungsten oxide nanowires and aluminum oxide nanowires. In a preferred embodiment, the nanometer metal wires in the conductive electrode material are metallic silver wires.

The "OLED: Organic Light Emitting Diode" described in this article is made of an extremely thin stacked device composed of two upper and lower electrodes sandwiching organic materials in the middle. Compared with inorganic light-emitting diodes, which mainly use metal as the light-emitting layer, organic light-emitting diodes use organic polymer materials as the light-emitting layer. Because the self-luminous nature of OLED does not require a backlight module, the resulting display can be lighter and thinner, and the organic material is suitable for making on a flexible substrate, which can make the panel have flexible characteristics. The transparent technical method of OLED technology is to use transparent conductors as electrodes, and the effect of transparent display can be achieved with the matching of the lower plate design. The aforementioned organic polymer materials used as the light-emitting layer are preferably: polythiophene (polythiophene), polyfluorene (polyfluorene, PF), poly (p-phenylene-vinylene)), polysilane, Polyacetylenes, polyvinylcarbazoles or their derivatives, such as poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene )-alt-2,7-(9,9-dioctylfluorene)] (Poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt -2,7-(9,9-dioctylfluorene)], PFN) or poly[9,9-bis{6(N,N-dimethylamino)hexyl}fluorene-co-2,5-thiophene (poly[ 9,9-bis{6(N,N-dimethylamino)hexyl}fluorene-co-2,5-thienylene, PFT), etc., but the present invention is not limited thereto. In a preferred embodiment, polyfluorene is used as the material of the organic light-emitting layer. The polyfluorene polymer has excellent photoelectric properties due to its unique conjugated structure, and is a blue light-emitting material. Example

Hereinafter, the present invention will be further described in detail and implementations, however, it should be understood that these implementations are only for helping to understand the present invention more easily, rather than limiting the scope of the present invention. [Laboratory equipment]

1. Vacuum synthesis system: the model is a glass vacuum synthesis unit, and the supplier is Kelin Enterprise Co., Ltd. 2. Electronic analyzer and precision balance: the model is ATX224, and the supplier is SHIMADZU. 3. Rotary decompression concentrator: the model is R-100, and the supplier is BUCHI. 4. Ultrasonic oscillating water tank: the model is DC200H, and the supplier is DELTA Company. 5. Vacuum oven: the model is DOV40, and the supplier is DENG YNG Company. 6. Nuclear magnetic resonance spectrometer ( ¹ H-NMR): the model is Fourier300, and the supplier is BRUKER. 7. Thermal analysis-infrared spectrometer (TG/FT-IR): the model is FT/IR-4600, and the supplier is JASCO. 8. Gel permeation chromatography (GPC): the model is RI-2031, plus, and the supplier is JASCO. 9. Thermogravimetric Analyzer (TGA): The model is TG-209, and the supplier is NETZSCH. 10. Dynamic Thermomechanical Analyzer (DMA): the model is DMS 6100, and the supplier is Tech Max. 11. Universal tensile testing machine: the model is QC508, and the supplier is Cometech. 12. Contact angle meter (Contact angle): the model is Phoenix300, and the supplier is SEO Company. 13. Optical microscope (OM): the model is QC508, and the supplier is Cometech. 14. Field-emission electron microscope (FE-SEM): the model is S4800, and the supplier is HITACHI. 15. Ultraviolet-visible spectrometer (UV-Vis): the model is V-730, and the supplier is JASCO. 16. Fluorescence spectrometer (PL): the model is Fluoromax, and the supplier is HORIBA. 17. Spectrophotometric luminance colorimeter (PR-670): the model is PR-670, and the supplier is SPECTRASCAN. Example 1 - self-healing copolymerized polymer material PDMS-MDI _x -TFB _1-x [synthesis method]

As shown in Figure 1, the self-healing copolymerized polymer material of the present invention uses bis(3-aminopropyl)-terminated polydimethylsiloxane (bis(3‐aminopropyl) ‐terminated poly(dimethylsiloxane)), diphenylmethane diisocyanate (4,4‐methylenebis(phenyl isocyanate)) and 1,3,5-benzene triformaldehyde (1,3,5-triformylbenzene), using condensation polymerization and regulation Polydimethylsiloxane polymers with self-healing effect were prepared in different proportions. The steps of the two-step method are described below.

The first step-synthesis of polydimethylsiloxane polymer prepolymer (PDMS-MDI): bis(3-aminopropyl) end-capped polydimethylsiloxane (NH ₂ -PDMS-NH ₂ ) Dissolve in chloroform solvent, add triethylamine as a catalyst, and stir for 30 minutes until completely dissolved. Dissolve diphenylmethane diisocyanate (MDI) in chloroform solvent and stir for 10 minutes until completely dissolved. Put the two reactants into liquid nitrogen respectively, and remove the moisture and oxygen in the solvent by freeze-vacuum drying three times, then extract the MDI solution with an airtight needle, slowly drop into the NH ₂ -PDMS-NH ₂ solution, and After reacting in the ice bath for 1 hour, the ice bath was removed, and the temperature was gradually returned to room temperature and reacted for 5 hours. After the reaction is over, slowly add the product to methanol, continue to stir for 12 hours, pour out the methanol and dissolve the precipitate with chloroform, remove the chloroform solvent by using a rotary decompression concentrator, and place it in a vacuum oven for 12 hours to obtain polydimethyl Silicone polymer prepolymer.

The second step - synthesis of polydimethylsiloxane self-healing copolymerized polymer material (PDMS-MDI _x -TFB _1-x ): Dissolve the first step product PDMS-MDI in chloroform solvent and stir for 30 minutes until completely dissolved. Dissolve 1,3,5-benzenetricarbaldehyde (TFB) in chloroform solvent and stir for 10 minutes until completely dissolved. Put the two reactants into liquid nitrogen respectively, and remove the water vapor and oxygen in the solvent by freeze-vacuum drying three times, then extract the TFB solution with an airtight needle, slowly drop into the PDMS-MDI solution, and react at room temperature for 6 After waiting for the reaction to finish, the self-healing copolymerized polymer material PDMS-MDI _x -TFB _1-x solution can be obtained.

Preparation of self-healing polymer elastomer film: Pour the synthesized PDMS-MDI _x -TFB _1-x solution into a Teflon mold, move it to an ultrasonic vibration tank for 30 minutes, and disperse the solution evenly in the Teflon mold. Dragon mold, and placed in a fume hood at room temperature for 12 hours to wait for the solvent to volatilize, then move to a vacuum oven to dry for 6 hours, and then it can be removed to obtain a self-healing polymer elastomer film. [Structural analysis] 1. ¹ H-NMR analysis

¹ H-NMR is used to identify the chemical shift of protons in different environments on the polymer structure, and then judge whether the polymer is successfully synthesized.

Using chloroform to dissolve the self-healing copolymer polymer material for d-solvent, using the special ¹ H signal on the functional group to identify the structure, and calculating the integral area to determine the molar ratio of the successful reaction between MDI and TFB.

Taking PDMS-MDI _0.4 -TFB _0.6 as an example, Figure 2 shows the ¹ H-NMR spectrum (CDCl ₃ ; δppm) of PDMS-MDI _0.4 -TFB _0.6 , the chemical shift is 7.24 ppm, which is the solvent signal of CDCl ₃ , and the chemical shift is 3.2 , 3.6 ppm are the CH ₂ signals of the reaction of PDMS terminal amine groups with MDI and TFB monomers respectively. As shown in Figure 3, the chemical shifts of 6.92 and 7.62 ppm are the reaction between the terminal amine group (-NH ₂ ) of PDMS and the isocyanate group (-NCO) of MDI to form a new urea group (-NH-C=O-NH-) The NH signal. The chemical shift of 8.15 ppm is the NH signal of the reaction of PDMS terminal amine group (-NH ₂ ) and TFB aldehyde group (-CHO) to form a new imine group (-C=NH), through the above ¹ H-NMR spectrum The signal can indicate that the self-healing copolymer polymer material has been successfully synthesized. 2. FT-IR spectral analysis

FT-IR spectroscopy is most commonly used in the identification of functional groups, using different functional groups to produce different vibration frequencies, analyzing the position of specific absorption peaks, and identifying the structure and type of functional groups.

Cut the sample into strips of 1 x 2 cm, and use a Fourier transform infrared spectrometer to scan from 400 to 4000 cm ^-1 to observe the characteristic absorption peaks of functional groups of self-healing copolymerized polymer materials. TG/FT-IR observation of hydrogen bond absorption peaks of functional groups of self-healing copolymerized polymer materials.

Please refer to Figure 4 for the following content. Taking PDMS-MDI _0.4 -TFB _0.6 as an example, the isocyanate group (-NCO) in the MDI monomer has a characteristic peak at 2260 cm ^-1 , and the aldehyde group (-CHO) in the TFB monomer It has its characteristic peak at 1680 cm ^-1 , and when the reaction is completed, there are no obvious characteristic peaks of -NCO and -CHO in the spectrum of PDMS-MDI _0.4 -TFB _0.6 , indicating that this self-healing copolymeric polymer material has been successfully synthesized.

Please refer to Figure 5, which are the FT-IR spectra of different proportions of self-healing copolymerized polymer materials, at 1635-1645 cm ^-1 and 3300-3350 cm ^-1 are the -C=O and - of the urea group, respectively The NH characteristic peak, 1650-1665 cm ^-1 is the -C=N characteristic peak of the imine group.

Please refer to Figure 6. It can be observed from the characteristic peak signal at 3300-3350 cm ^-1 that when the proportion of MDI increases, the -NH signal of the urea group gradually increases, indicating that the functional groups that can generate hydrogen bonds increase. When the proportion of TFB increases and the proportion of MDI When it decreases, the -C=O signal of 1635-1645 cm ^-1 urea group gradually weakens, and the -C=N signal of 1650-1665 cm ^-1 imine group gradually increases, indicating that the reversible covalent bond with self-repair increases . 3. WAXD analysis

The sample is prepared into a thin film, and the scanning angle ranges from 10º to 40º. It is observed that the self-healing copolymerized polymer elastomer has no obvious diffraction peaks, and it is judged as an amorphous polymer. [Gel Permeation Chromatography (GPC) Molecular Weight Identification]

Gel Permeation Chromatography (GPC) is a common method used to measure the molecular weight of polymers. Different proportions of self-healing copolymerized polymer materials PDMS-MDI _x -TFB _1-x are dissolved in THF as the GPC mobile phase solvent , the preparation concentration was 10mg/ml, and injected into GPC after completely dissolved, the column temperature was set to 40°C, the analysis time was 30 minutes, and the flow rate was 1 ml/min. Wait 30 minutes for molecular weight data.

Please refer to Table 1. When the proportion of MDI increases, the molecular weight increases gradually, indicating that PDMS has better reactivity with MDI, and poor reactivity with TFB, and the PDI range is between 1.4-1.7. When the PDI value is too large, it means that the molecular weight distribution is too large and the length of the molecular chain is uneven. This phenomenon will cause the self-repairing group to be separated and difficult to recombine, resulting in a decline in the self-repairing effect. When the PDI value is greater than 2, it will show poor self-repair. Repair effect, PDI value of about 1.5 has a good self-repair effect.

表1 [熱穩定性分析]

Table 1 [Thermal Stability Analysis]

Thermal cracking temperature (T _d ) is measured by thermogravimetric analyzer TGA, and thermal cracking temperature is generally used to represent the thermal stability of the polymer. Observe the thermogravimetric analysis curve, when the mass loss is 5%, it is the thermal cracking temperature (degradation temperature, T _d5% ).

Take 5 to 10 mg of sample and place it in a ceramic dish, in an argon atmosphere at a heating rate of 10 degrees per minute from 25 to 900 ºC, and observe the change in temperature to weight loss, residual weight, the temperature range of the fastest weight loss and weight Loss of 5% pyrolysis temperature.

As shown in Figure 7, it is a TGA curve of different proportions, and the test temperature range is 25-900°C. Table 2 below shows the thermal solution temperatures of different ratios of self-healing copolymerized polymer materials. According to Table 2, when the proportion of MDI decreases and the proportion of TFB increases, the thermal cracking temperature will increase with the proportion of TFB. There are two reasons: (1) TFB has three reactive functional groups, when the three functional groups When the reaction is complete, the chemical cross-linking will produce a network structure and the T _d will increase; (2) when the proportion of TFB increases, it means that the proportion of MDI decreases, and the number of reversible covalent bonds will be more than the number of hydrogen bonds. It belongs to the first-order bond and has higher bond energy, which leads to an increase in T _d . Therefore, adding TFB can improve the thermal stability of polymers.

[玻璃轉移溫度分析] Table 2

[Glass transition temperature analysis]

The glass transition temperature (T _g ) is expressed by measuring the storage modulus, loss modulus and damping (Tanδ) signal with a mechanical dynamic thermal analyzer DMA.

Cut the prepared sample film into 4 cm long, 1 cm wide, and 0.5 mm thick sample specimens, and use the tensile mode to measure, the measurement temperature range is -150 ºC to 30 ºC, the heating rate is 5 ºC/min, the static force : The power is 1: 0.9, 1Hz.

Figure 8 is the DMA curves of self-healing copolymerized polymer materials with different proportions. Table 3 shows the T _g points of different ratios of self-healing copolymer polymer materials. As shown in Figure 8 and Table 3, when the TFB ratio increases, the T _g point of the self-healing copolymerized polymer material gradually decreases. When the T _g point is lower, it means that the polymer chain is easier to move, enabling self-healing. The repairing functional group is easy to touch to achieve the effect of self-repairing.

表3 [機械性質分析]

Table 3 [Mechanical Property Analysis]

When the polymer material is subjected to a tensile test, the polymer material is given an external force to stretch to produce a change in appearance and size. The change in appearance is called strain. At this time, the force that produces resistance inside the polymer material is called stress. Young’s The modulus is used to describe the ability of polymer materials to resist deformation. According to Hooke's law, within the elastic limit of the object, the stress and strain become proportional, and the ratio of the two is Young's modulus.

In self-healing materials, the stress and strain measured by the tensile test are usually used to describe the characteristics of the self-healing material, and the ratio of the tensile stress before the polymer has not been damaged to the tensile stress after the polymer is repaired is called repair. Efficiency (Healing efficiency).

The invention uses a universal tensile testing machine to test mechanical properties such as yield point, elongation, Young's modulus, and maximum breaking stress. The sample film was cut into a sample with a length of 3 cm, a width of 1 cm, and a thickness of 0.5 mm, and was measured at a tensile rate of 50 mN/min.

As shown in Figure 9, when the ratio of MDI increases, the MDI structure has a higher tensile stress and lower elongation rate because the double benzene ring in the MDI structure is more rigid than the TFB single benzene ring structure. On the contrary, when the ratio of TFB increases, it has higher elongation rate and lower tensile stress.

Please refer to Figure 10. In a preferred implementation, PDMS-MDI _0.4 -TFB _0.6 with moderate hardness and softness is selected as the material discussed below for subsequent applications, because this self-healing copolymer polymer material has Therefore, we tested different repair times at room temperature and found that when repaired at room temperature for 3 hours, the repair efficiency can reach 80%, but as the repair time increases, the stress will not increase significantly , will only slightly increase the elongation rate. This phenomenon shows that after 3 hours of repairing at room temperature, the material can produce self-repairing groups. Repair efficiency.

Please refer to FIG. 11 . In a preferred embodiment, the self-healing is observed with an optical microscope. After being placed at room temperature for 3 hours for repairing, the cut scars have completely disappeared, indicating that the repairing has been completed. In addition to self-healing at room temperature, self-healing tests of this self-healing copolymerized polymer material were also carried out in different environments, and the self-healing tests were performed in -10°C, 25°C water, 60°C water and NaCl aqueous solution. In the case of restoration, Figure 12 is a self-healing stress-strain curve under different environmental conditions. It can be observed that a certain degree of restoration effect can be achieved under various external environments. As shown in Figure 13 and Table 4, self-healing tests were performed on PDMS-MDI _0.4 -TFB _0.6 materials in a preferred embodiment, and the self-healing efficiency reached over 75% under different environmental conditions.

表4

Table 4

The following examples describe preferred exemplary applications of the self-healing copolymerized polymer material of the present invention. Example 2 - Luminescent material

The luminescent material of this embodiment is the aforementioned self-repairable copolymerized polymer material mixed with perovskite quantum dots. In a preferred embodiment, the self-healing copolymerized polymer material is dissolved in toluene to prepare a 15 wt% solution, and a 10 mg/ml perovskite quantum dot solution is added and mixed uniformly to prepare into a self-healing perovskite quantum dot film.

Please refer to Figure 14. The tensile test of the film shows that the mechanical properties of the self-healing copolymerized polymer film will not be weakened by the mixing of perovskite quantum dots, and the self-healing properties of the mixing of perovskite quantum dots The efficiency of the copolymerized polymer film can reach 80% after repair, and it can be stretched, bent, twisted, etc., as shown in Figure 15.

Measure the self-healing perovskite quantum dot film with a UV-visible spectrometer and a fluorescence spectrometer, see Figure 16. When the film is damaged and repaired, the UV-visible spectrophotometry of the perovskite quantum dot will not be affected UV-Vis absorption peak signal and photoluminescence (PL) signal lead to weakening or shifting phenomenon.

Generally speaking, perovskite materials are easily deliquified by moisture and lose optical properties, but the self-healing copolymerized polymer material of the present invention has PDMS as the main structure and is hydrophobic. The self-healing perovskite quantum dot film of this embodiment was soaked in water, and the brightness was not significantly weakened by naked eyes. In addition, measured by a fluorescence spectrometer, the PL intensity weakens with the time soaked in water, but still maintains a certain intensity, as shown in Figure 17. In order to prove that the self-healing copolymer polymer material is hydrophobic, a contact angle meter was used to measure it. As shown in Figure 18, the measured contact angle is 103°, which shows that the self-healing copolymer polymer material of the present invention The material is indeed a hydrophobic material. Therefore, the self-healing copolymer polymer material of the present invention is hydrophobic, which can protect the perovskite quantum dots from losing their original optical properties due to soaking in water. Example 3 - LED backlit display

In this embodiment, the self-healing perovskite quantum dot thin film of Embodiment 2 is applied to a backlight display.

Taking the production of white LED chips as an example, first, self-healing copolymerized polymer materials are mixed with green and red perovskite quantum dots, and green and red self-healing perovskite quantum dot films are prepared. Next, please refer to FIG. 19 below. With the blue LED chip 22 as the base, the aforementioned green self-healing perovskite quantum dot film 21 is used as the first layer, and the aforementioned red self-healing perovskite quantum dot film 20 is stacked as the second layer. two layers, and adjusting the thickness of the film, the white LED chip 24 can be produced.

Use the PR-670 spectroscopic luminance colorimeter to measure, as shown in Figure 20, the emission spectrum that produces white light can be observed, and see Figure 21, the CIE color coordinate diagram shows that the chromatic light is located in the white light area, indicating that it has been successfully prepared White LED backlit display. Example 4 - Conductive Electrode Material

In this embodiment, the thin film made of the self-healing copolymer polymer material in Embodiment 1 is mixed with nanometer metal wires to make a conductive electrode material. In one embodiment, the PDMS-MDI _0.4 -TFB _0.6 film is coated with silver nano wire solution, placed at room temperature for drying, and then coated with liquid metal gallium to complete the fabrication of self-healing conductive electrodes.

Since flexible electronic components need to be bent frequently, in this embodiment, the self-healing conductive electrode is subjected to 100 bending tests, and the resistance value change is measured at the same time. After testing, it can be observed that after 100 times of bending, the sheet resistance value is not higher than 20 ohm/cm ² , which shows that the self-healing conductive electrode will not lose its electrical properties due to repeated bending. When the self-healing copolymer polymer moves, the silver nanowires will be partially embedded in the polymer, so that the electrode is not easy to fall off and still has conductivity. Example 5 - Organic Light Emitting Diodes

In this embodiment, an organic light-emitting layer and the conductive electrode material in Embodiment 4 are made into an organic light-emitting diode (OLED). In this embodiment, polyfluorene (PF) is used as the organic light emitting material, which is a blue light emitting material. [Production method]

Prepare 1 wt% polyethylene glycol (PEO) solution in DMF, add poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS) at a ratio of 1:20, and stir well to obtain Electron transport layer solution; prepare 1 wt% PF solution as the emissive layer solution.

After placing the PDMS-MDI _0.4 -TFB _0.6 film as in Example 1 in an oxygen plasma machine for 2 minutes, PEDOT:PSS/PEO was coated on the aforementioned PDMS-MDI by spin coating at 500 rpm/10s and then at 1000 rpm/20s _0.4 - TFB _0.6 film, and heated at 70°C/10min. Then apply the PF solution by spin coating at 1000 rpm/30, and heat at 80°C/10min.

As shown in Figure 22, another PDMS-MDI _0.4 -TFB _0.6 film is coated with silver nanowire solution to form a conductive electrode material 311, placed at room temperature and waited to dry, and then coated with liquid metal gallium 312 to complete self-healing Fabrication of the conductive electrode 31 (i.e. embodiment 4).

Combining the aforementioned self-healing conductive electrode and the aforementioned light-emitting layer into a self-healing organic light-emitting diode. As shown in FIG. 22 , in a preferred embodiment, the organic light emitting diode 30 has a structure of conductive electrode layer 31//light emitting layer 32/electron transport layer 33/self-healing copolymerized polymer material layer 34.

As shown in Figure 23, after the current is applied, the self-healing organic light-emitting diode successfully emits blue light, and it is measured with PR-670, and it can be observed that it starts to emit light at 10V. Next, test whether the self-healing organic light-emitting diode can continue to emit light after being repaired. After the self-healing conductive electrode is cut, the original light-emitting position is instantly extinguished, which is due to the nano-silver wires being unable to touch each other after cutting, making the electrode continue to be unable to conduct electricity. After waiting for 3 hours for the electrode to be repaired, the self-repairing copolymerized polymer chain migrates and drives the nano silver wire to move along with it during the repair, so that the nano silver wire touches again to restore conductivity and emit light again. Figure 24. After self-healing, it was measured with PR-670, and it was found that the brightness after healing was close to the brightness of self-healing organic light-emitting diodes before cutting.

In addition, in order to test whether the points and surfaces of the self-healing organic light emitting diode can be illuminated, the self-healing organic light emitting diode can be successfully illuminated by pressing with the tip of the tweezers and the wrench respectively.

Example 6 - Flexible Light Emitting Electronic Components

Since the self-healing copolymerized polymer material of the present invention has stretchability and bendability, flexible light-emitting electronic components can be prepared by applying the organic light-emitting diode in Example 5 through this characteristic.

Please refer to FIG. 25 , which is a schematic diagram of a self-healing flexible light-emitting electronic component 10, which has a conductive electrode layer 13/insulating film 14/light-emitting layer 15/electron transport layer 16/self-healing copolymerized polymer material layer 17/insulating film 14 The structure. That is, as in Embodiment 5, only after a non-conductive insulating film (for example: PET film) 14 is pasted on both sides of the light-emitting layer (for example: PF layer) 15, and then covered with the self-healing conductive electrode 13 of Embodiment 4, A self-healing flexible light-emitting electronic component 10 is prepared.

The self-healing flexible light-emitting electronic component was pasted on the finger, and after the current was applied, the self-healing flexible light-emitting electronic component did not emit light. However, when the finger is bent, the self-healing flexible light-emitting electronic component emits light after being energized due to the successful contact between the light-emitting layer and the electrode. Therefore, the self-healing flexible light-emitting electronic component is successfully prepared.

To sum up, the present invention has successfully prepared a novel self-healing copolymerized polymer material PDMS-MDI _x -TFB _1-x , and provides various applications. The present invention has the following advantages:

1. When the proportion of MDI in PDMS-MDI _x -TFB _1-x increases, the increase of -NH signal can indicate the increase of functional groups that generate hydrogen bonds. When the proportion of TFB increases, the increase of -C=N signal indicates the generation of reversible covalent bonds The functional group increases. The PDMS-MDI _x -TFB _1-x of the present invention has non-covalent hydrogen bonds and reversible covalent imine bonds, and contains two kinds of self-healing functional groups. Hydrogen-bonded self-healing requires the use of increased temperature to break hydrogen bonds. When the temperature is removed, the urea groups that generate hydrogen bonds rebond to produce self-healing. In the past, reversible covalent self-healing also required heating to generate a reaction, but the reversible imine bond of the present invention can undergo a reversible reaction at room temperature, so when the unbonded amine group touches the aldehyde group, that is Can generate reversible imine bonds for self-healing.

2. The PDMS-MDI _x -TFB _1-x of the present invention has excellent thermal stability, and when the proportion of TFB increases, the thermal cracking temperature rises gradually.

3. When the proportion of TFB in PDMS-MDI _x -TFB _1-x increases, T _g gradually decreases. This phenomenon indicates that the polymer chain is easier to move, so that the functional groups capable of self-repair can be easily touched to achieve the effect of self-repair , so a higher proportion of TFB has a better self-healing efficiency.

4. Due to the rigidity of the MDI structure, PDMS-MDI _x -TFB _1-x has higher tensile stress and lower elongation when it has a high proportion of MDI, and vice versa when it has a high proportion of TFB.

5. The present invention has been tested to perform self-repair at different times at room temperature, and found that the repair efficiency can reach 80% within 3 hours, and it can also perform self-repair in various environments.

6. The PDMS-MDI _x -TFB _{1-x is} mixed with perovskite quantum dots, because the hydrophobicity of PDMS as the main structure can protect the perovskite quantum dots from loss of optical properties due to water vapor attack.

7. The present invention mixes PDMS-MDI _x -TFB _1-x with perovskite quantum dots and puts them into blue LED chips, successfully producing a self-healing white LED backlight display.

8. The present invention utilizes the addition of nanometer metal wires into PDMS-MDI _x -TFB _1-x to produce self-healing conductive electrodes, and uses organic polymers as light-emitting materials to successfully produce organic light-emitting diodes. After testing, the self-healing conductive electrode is cut, and after waiting for repair, the organic light-emitting diode can be made to shine again, and the self-healing organic light-emitting diode is successfully produced.

9. Improve the aforementioned self-healing organic light-emitting diode with insulating materials at both ends to block the electrode and the light-emitting layer, stick it to the finger and then bend it, so that the electrode and the light-emitting layer will be in contact with the light-emitting layer and glow after being energized to produce a self-healing flexible electronic component .

Herein, all ranges provided are intended to include each specific range within the given range as well as combinations of subranges between the given ranges. Additionally, unless otherwise stated, all ranges provided herein include the endpoints of the stated range. Thus, the range 1-5 specifically includes 1, 2, 3, 4, and 5, and sub-ranges such as 2-5, 3-5, 2-3, 2-4, 1-4, and so on.

The term "comprising or comprising" referred to herein means not excluding the existence or addition of one or more other components, steps, operations and/or elements to the described components, steps, operations and/or elements. The terms "comprising", "comprising", "containing", "comprising", and "having" described herein are interchangeable and not limiting. "About or close to" or "substantially" means a value or range that is close to the specified error to avoid illegal or unfair use by any unreasonable third party to understand the precise or absolute value disclosed in the present invention. "A" means one or more than one (ie, at least one) of the grammatical object of the thing.

The present invention has been described in detail above, but the above is only a preferred embodiment of the present invention, and should not limit the scope of the present invention with this, that is, all the equivalents of the scope of the patent application for the present invention Changes and modifications should still fall within the scope of the patent coverage of the present invention.

10: Flexible light-emitting electronic components

13: Conductive electrode layer

14: insulating film

15: Luminous layer

16: Electron transport layer

17: Self-healing copolymerized polymer material layer

20: Red self-healing perovskite quantum dot film

21: Green self-healing perovskite quantum dot film

22:Blue LED chip

24:White LED chip

30: Organic Light Emitting Diodes

31: Conductive electrode layer

311: Conductive electrode material

312: Gallium

32: luminescent layer

33: Electron transport layer

34: Self-healing copolymerized polymer material layer

Fig. 1 is a schematic diagram of a synthesis method of PDMS-MDI _0.4 -TFB _0.6 according to a preferred embodiment of the present invention.

Fig. 2 is an NMR spectrum of PDMS-MDI _0.4 -TFB _0.6 according to a preferred embodiment of the present invention.

Fig. 3 is a partial NMR spectrum of PDMS-MDI _0.4 -TFB _0.6 according to a preferred embodiment of the present invention.

Fig. 4 is the FT-IR functional group identification of PDMS-MDI _0.4 -TFB _0.6 according to a preferred embodiment of the present invention.

FIG. 5 is an FT-IR spectrum of a self-healing copolymerized polymer material with different ratios according to a preferred embodiment of the present invention.

Fig. 6 is the FT-IR spectra of self-healing copolymeric polymer materials -NH, -C=N, -C=O with different proportions according to a preferred embodiment of the present invention.

FIG. 7 is a TGA curve of different ratios of self-healing copolymerized polymer materials according to a preferred embodiment of the present invention.

FIG. 8 is a DMA curve of a self-healing copolymerized polymer material with different ratios according to a preferred embodiment of the present invention.

FIG. 9 is a stress-strain curve of self-healing copolymer polymer materials with different proportions according to a preferred embodiment of the present invention.

FIG. 10 is a stress-strain graph of self-healing at room temperature of a self-healing copolymer polymer material according to a preferred embodiment of the present invention.

FIG. 11 is an optical microscope image of self-healing of a self-healing copolymerized polymer material at room temperature according to a preferred embodiment of the present invention.

Fig. 12 is a self-healing stress-strain curve of the self-healing copolymerized polymer material in different environmental conditions according to a preferred embodiment of the present invention.

FIG. 13 is a graph of self-healing efficiency of a self-healing copolymerized polymer material under different environmental conditions according to a preferred embodiment of the present invention.

Fig. 14 is a stress-strain graph of a self-healing perovskite quantum dot film according to a preferred embodiment of the present invention.

Fig. 15 is a bending and torsion diagram of a self-healing perovskite quantum dot film after repairing according to a preferred embodiment of the present invention.

Fig. 16 is a UV-Vis and PL diagram of a self-healing perovskite quantum dot thin film according to a preferred embodiment of the present invention.

Fig. 17 is a PL diagram of a self-healing perovskite quantum dot film soaked in water according to a preferred embodiment of the present invention.

Fig. 18 is the contact angle of the self-healing perovskite quantum dot film according to a preferred embodiment of the present invention.

FIG. 19 is a schematic structural diagram of a white LED backlight display according to a preferred embodiment of the present invention.

Fig. 20 is an electroluminescence spectrum diagram of a white LED backlight display according to a preferred embodiment of the present invention.

FIG. 21 is a CIE coordinate diagram of a white LED backlight display according to a preferred embodiment of the present invention.

Fig. 22 is a schematic diagram of the structure of a self-healing organic light emitting diode according to a preferred embodiment of the present invention.

Fig. 23 is an EL diagram of a self-healing organic light emitting diode according to a preferred embodiment of the present invention.

FIG. 24 is an EL diagram of a self-healing organic light-emitting diode after repairing according to a preferred embodiment of the present invention.

Fig. 25 is a schematic cross-sectional view of a self-healing flexible light-emitting electronic component according to a preferred embodiment of the present invention.

none.

Claims (11)

A self-healing copolymerized polymer material, which is a copolymer of polydimethylsiloxane (PDMS), diphenylmethane diisocyanate (MDI) and 1,3,5-benzenetricarbaldehyde (TFB) The polymeric polymer PDMS-MDI _x -TFB _1-x , wherein _x is 0.1-0.9, and it has a PDI (Polymer dispersion index, polymer dispersion index) of 1.4-1.7. The copolymerized polymer material according to claim 1, wherein the _x is 0.4. The copolymerized polymer material according to claim 1, which has self-healing functional groups of hydrogen bonds and imine bonds. The copolymerized polymer material according to any one of Claims 1 to 3 has a glass transition temperature (T _g ) of -110 to -130°C. A method for manufacturing a self-healing copolymerized polymer material according to any one of claims 1 to 4, comprising: (1) bis(3-aminopropyl)-terminated polydimethylsilane (bis(3- aminopropyl)-terminated poly(dimethylsiloxane), NH ₂ -PDMS-NH ₂ ) and diphenylmethane diisocyanate (4,4-methylenebis(phenyl isocyanate), MDI) are polymerized to obtain PDS-MDI; and (2) the PDS -MDI is polymerized with 1,3,5-benzenetriformaldehyde (1,3,5-triformylbenzene, TFB) to obtain PDMS-MDI-TFB. A luminescent material, comprising the copolymerized polymer material mixed with perovskite quantum dots according to any one of claims 1 to 4. A white LED backlight display, comprising a blue LED chip, and two layers of the luminescent material according to claim 6 respectively superimposed on it, wherein the two layers of luminescent material are respectively copolymerized polymers The material is mixed with green perovskite quantum dots, and the copolymerized polymer material is mixed with red perovskite quantum dots. A conductive electrode material comprising the copolymerized polymer material mixed with nano metal wires according to any one of claims 1 to 4. The conductive electrode material according to claim 8, wherein the nanometer metal wires are metallic silver wires. An organic light-emitting diode, which comprises a light-emitting layer and the conductive electrode material according to claim 8 or 9 as an electrode. A flexible light-emitting electronic component, which includes the organic light-emitting diode as described in claim 10, and an insulating film is used to block the light-emitting layer and the electrode, and the insulating film does not completely cover the light-emitting layer, so that the flexible In light-emitting electronic components, the light-emitting layer is in contact with the electrode.

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